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United States Patent |
5,104,674
|
Chen
,   et al.
|
April 14, 1992
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Microfragmented ionic polysaccharide/protein complex dispersions
Abstract
Microfragmented ionic polysaccharide/protein complex dispersions which are
suitable for use as fat substitute compositions in food products such as
ice cream, salad dressings, dips, spreads and sauces and methods for
preparing such dispersions and food products.
Inventors:
|
Chen; Wehn-Sherng (Glenview, IL);
Henry; George A. (Wilmette, IL);
Gaud; Susan M. (Evanston, IL);
Miller; Mark S. (Arlington Heights, IL);
Kaiser; John M. (Glenview, IL);
Balmaceda; Estela A. (Winnetka, IL);
Morgan; Ronnie G. (Northbrook, IL);
Baer; Cynthia C. (Arlington Heights, IL);
Borwankar; Rajendra P. (Elmhurst, IL);
Hellgeth; Lorraine C. (Chicago, IL);
Strandholm; John J. (Morton Grove, IL);
Hasenhuettl; Gerard L. (Highland Park, IL);
Kerwin; Phillip J. (Wilmette, IL);
Chen; Chyi-Cheng (Morton Grove, IL);
Kratochvil; John F. (Oak Brook, IL);
Lloyd; Wennie L. (Marengo, OH);
Eckhardt; Gerard (Bay Shore, NY);
De Vito; Adam P. (Chicago, IL);
Heth; Alice A. (Evanston, IL)
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Assignee:
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Kraft General Foods, Inc. (Glenview, IL)
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Appl. No.:
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548950 |
Filed:
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July 20, 1990 |
PCT Filed:
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April 28, 1989
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PCT NO:
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PCT/US89/01813
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371 Date:
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July 27, 1990
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102(e) Date:
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July 27, 1990
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PCT PUB.NO.:
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WO89/10068 |
PCT PUB. Date:
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November 2, 1989 |
Current U.S. Class: |
426/573; 426/496; 426/565; 426/575; 426/576; 426/577; 426/589; 426/602; 426/610; 426/611; 426/613; 426/653; 426/656; 426/657; 426/658 |
Intern'l Class: |
A23L 001/05 |
Field of Search: |
426/573,574,575,496,576,577,610,611,646,602,613,653,658,656,657,589,565
|
References Cited
U.S. Patent Documents
3353966 | Nov., 1967 | Hagenberg et al. | 426/610.
|
3600186 | Aug., 1971 | Mattson et al. | 426/611.
|
4559233 | Dec., 1985 | Chen et al. | 426/104.
|
4563360 | Jan., 1986 | Soucie et al. | 426/656.
|
4762726 | Aug., 1988 | Soucie et al. | 426/602.
|
Primary Examiner: Hunter; Jeanette
Attorney, Agent or Firm: Fitch, Even, Tabin & Flannery
Parent Case Text
CROSS-REFERENCES TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. application Ser. No.
292,568 filed Dec. 30, 1988, now abandoned, which is a
continuation-in-part of U.S. patent application Ser. No. 188,283 filed
Apr. 29, 1988 now abandoned, and U.S. patent application Ser. No. 177,184,
now U.S. Pat. No. 4,885,179, filed Apr. 4, 1988, now abandoned, which is a
continuation-in-part of U.S. patent application Ser. No. 024,507 filed as
PCT application US85/01265 on Jul. 1, 1985, which entered national stage
in the United States on Mar. 1, 1987, now U.S. Pat. No. 4,762,726, which
is a continuation-in-part of U.S. patent application Ser. No. 567,096
filed Dec. 30, 1983, now U.S. Pat. No. 4,563,360, and U.S. patent
application Ser. No. 567,277 filed Dec. 30, 1983, now U.S. Pat. No.
4,559,233, and is a continuation-in-part of U.S. application Ser. No.
081,115 filed Aug. 3, 1987, abandoned in favor of continuation-in-part
application Ser. No. 307,069 filed Feb. 6, 1989, now abandoned which is a
continuation-in-part of U.S. application Ser. No. 658,618 filed Oct. 9,
1984, now U.S. Pat. No. 4,684,533, which are incorporated by reference
herein.
Claims
We claim:
1. A method for producing a microfragmented anisotropic xanthan/protein
complex dispersion comprising the steps of forming an aqueous suspension
of molecularly intimately complexed xanthan/protein fibers comprising at
least 7 weight percent of xanthan gum based on the total solids weight of
said fibers,
conducting said aqueous fiber suspension through a zone of high shear to
fragment the fibers under sufficient conditions of shear and duration to
reduce substantially all of said fibers to xanthan/protein complex
microfragments having a maximum dimension of less than about 15 microns.
2. A method in accordance with claim 1 wherein said fiber suspension
comprises from about 1 to about 10% by weight of said xanthan/protein
complex fibers.
3. A method in accordance with claim 1 wherein the microfragment dispersion
is concentrated by centrifugation at a pH substantially approximating the
isoelectric point of the fibrous complex.
4. A method in accordance with claim 1 wherein said microfragmented
dispersion is concentrated by evaporation of at least a portion of the
aqueous phase.
5. A method in accordance with claim 1 wherein said xanthan/protein fibers
are heated to stabilize substantially all of said xanthan/protein complex.
6. A method for producing microfragmented ionic polysaccharide/protein
complex dispersions comprising the steps of forming an aqueous suspension
of a syneresed molecularly intimately entangled complexed ionic
polysaccharide/protein complex precipitate, conducting said syneresed
complex suspension through a zone of high shear to fragment the complex
under sufficient conditions of shear and duration to reduce substantially
all of said complex to ionic polysaccharide/protein complex microfragments
having a maximum dimension of less than about 15 microns.
7. A method for producing a microfragmented ionic polysaccharide/protein
complex dispersion in accordance with claim 6 wherein said dispersion is
an anisotropic carboxymethyl cellulose/protein complex dispersion
comprising the steps of forming an aqueous suspension of molecularly
intimately complexed carboxymethyl cellulose/protein fibers comprising at
least 10 weight percent of carboxymethyl cellulose gum based on the total
solids weight of said fibers, conducting said aqueous fiber suspension
through a zone of high shear to fragment the fibers under sufficient
conditions of shear and duration to reduce substantially all of said
fibers to carboxymethyl cellulose/protein complex microfragments having a
maximum dimension of less than about 15 microns.
8. A method in accordance with claim 7 wherein said fiber suspension
comprises from about 1 to about 10% by weight of said carboxymethyl
cellulose/protein complex fibers, wherein said carboxymethyl
cellulose/protein fibers are heated to stabilize substantially all of said
carboxymethyl cellulose/protein complex, and wherein the microfragment
dispersion is concentrated by centrifugation at a pH substantially
approximating the isoelectric point of the fibrous complex, or by
evaporation of at least a portion of the aqueous phase.
9. A method for producing a microfragmented ionic polysaccharide/protein
complex dispersion in accordance with claim 6 wherein said dispersion is
an anisotropic carrageenan/protein complex dispersion comprising the steps
of forming an aqueous suspension of molecularly intimately complexed
carrageenan/protein fibers comprising at least 10 weight percent of
carrageenan based on the total solids weight of said fibers, conducting
said aqueous fiber suspension through a zone of high shear to fragment the
fibers under sufficient conditions of shear and duration to reduce
substantially all of said fibers to carrageenan/protein complex
microfragments having a maximum dimension of less than about 15 microns.
10. A method in accordance with claim 9 wherein said fiber suspension
comprises from about 1 to about 10% by weight of said carrageenan/protein
complex fibers, wherein said carrageenan/protein fibers are heated to
stabilize substantially all of said carrageenan/protein complex, and
wherein the microfragment dispersion is concentrated by centrifugation at
a pH substantially approximating the isoelectric point of the fibrous
complex or by evaporation of at least a portion of the aqueous phase.
11. A method in accordance with claim 6 wherein said complex suspension
comprises from about 1 to about 10% by weight of said ionic
polysaccharide/protein complex fibers.
12. A method in accordance with claim 6 wherein the microfragmented
dispersion is concentrated by centrifugation at a pH of less than about
4.5.
13. A method in accordance with claim 6 wherein the microfragment
dispersion is concentrated by centrifugation at a pH substantially
approximating the isoelectric point of the complex.
14. A method in accordance with claim 6 wherein said centrifugation
concentration is enhanced by providing an effective concentration of one
or more edible polyvalent cations in said aqueous dispersion.
15. A method in accordance with claim 6 wherein said microfragment
dispersion is concentrated by evaporation of at least a portion of the
aqueous phase by thin film swept surface evaporation under subatmospheric
conditions.
16. A method in accordance with claim 6 wherein said ionic
polysaccharide/protein complex is heated to stabilize substantially all of
said ionic polysaccharide/protein complex.
17. A method in accordance with claim 6 wherein said microfragments are
coated, at least in part, with calcium alginate, or calcium pectinate.
18. A method in accordance with claim 6 wherein said complex is a
thermoreversible gel of kappa carrageenan and gelatin.
19. A method in accordance with claim 7 wherein said protein is partially
protease-hydrolysed.
20. A method for preparing a smooth, creamy dispersion of ionic
polysaccharide/protein complex particles of very small size comprising the
steps of forming an aqueous complex generating solution of a solubilized
protein component and a complexing ionic polysacchrride component for the
protein component, comprising from about 1 to about 30 weight percent
solids based on the toal weight of the solution, providing a hydrophobic
working liquid which is immiscible with the aqueous complex generating
solution, forming a water-in-oil liquid emulsion of the
aqueous-complex-generating solution in the hydrophobic working liquid,
adjusting the pH of the emulsified aqueous complex-generating solution
emulsified in the hydrophobic working liquid to form precipitated complex
particles in the emulsified aqueous phase and separating the precipitated
complex particles from the hydrophobic liquid to provide a
polysaccharide/protein complex having a very small particle size.
21. A method for manufacturing edible lambda carrageenan/protein complex
fibers comprising the steps of providing an aqueous fiber generating
solution comprising a solubilized edible protein component and a
solubilized lambda carrageenan component, the weight ratio of said
carrageenan to said protein component being in the range of from about 1:2
to about 1:15 and wherein the total weight of said solubilized edible
protein component and said solubilized lambda carrageenan component is in
the range of from about 0.1 to about 8 weight percent, based on the total
weight of said aqueous fiber generating solution, adjusting the pH of the
fiber generating solution to the isoelectric point of an insoluble lambda
carrageenan/protein complex while mixing said fiber generating solution to
precipitate carrageenan/protein complex fibers and provide a whey
solution, and separating the fibers from the whey solution.
22. A method for manufacturing edible carboxymethyl cellulose/protein
complex fibers comprising the steps of providing an aqueous fiber
generating solution comprising a solubilized edible protein component and
a solubilized carboxymethyl cellulose component having a degree of
substitution of about 0.9, the weight ratio of said carboxymethyl
cellulose component to said protein component being in the range of from
about 1:2 to about 1:15 and wherein the total weight of said solubilized
edible protein component and said solubilized carboxymehtyl cellulose
component is in the range of from about 0.1 to about 8 weight percent,
based on the total weight of said aqueous fiber generating solution,
adjusting the pH of the fiber generating solution to the isoelectric point
of an insoluble carboxymethyl cellulose/protein complex while mixing said
fiber generating solution to precipitate carboxymethyl cellulose/protein
complex fibers and provide a whey solution, and separating the fibers from
the whey solution.
23. An aqueous, microfragmented ionic polysaccharide/protein complex
dispersion comprising from about 1 to about 50 weight percent of an
insolubilized, hydrated, microfragmented ionic polysaccharide/protein
complex discontinuous phase dispersed throughout a continuous aqueous
phase, said discontinuous microfragmented ionic polysaccharide/protein
complex phase comprising irregularly shaped microfragments of a hydrated
complex having an ionic polysaccharide to protein weight ratio in the
range of from about 2:1 to about 1:15, said ionic polysaccharide/protein
microfragments having a particle size distribution such that substantially
all of said microfragments have a maximum dimension of less than about 15
microns.
24. A microfragmented ionic polysaccharide/protein complex dispersion in
accordance with claim 23 wherein said complex is a syneresed, molecularly
intimately entangled interaction product of an ionic polysaccharide and a
protein.
25. A microfragmented ionic polysaccharide/protein complex dispersion in
accordance with claim 24 wherein said ionic polysaccharide is xanthan,
carboxy methyl cellulose, carrageenan, gellan, chitosan, pectin, alginate
or mixture thereof, and wherein at least about 90 percent by weight of
hydrated microfragments of the aqueous dispersion have a volume of less
than 5.times.10.sup.10 cubic centimeters and have a maximum linear
dimension of about 7 microns.
26. A microfragmented syneresed ionic polysaccharide/protein complex
dispersion in accordance with claim 24 comprising microfragments having a
mean maximum dimension in the range of from about 2 to about 10 microns.
27. A microfragmented syneresed ionic polysaccharide/protein complex
dispersion in accordance with claim 24 wherein said ionic
polysaccharide/protein complex is a whey protein complex.
28. A microfragmented ionic polysaccharide/protein complex dispersion in
accordance with claim 23 wherein said ionic polysaccharide/protein complex
is an ionic polysaccharide/egg albumen complex.
29. A microfragmented ionic polysaccharide/protein complex dispersion in
accordance with claim 23 wherein said ionic polysaccharide/protein fibers
are heated to stabilize substantially all of said ionic
polysaccharide/protein complex.
30. An aqueous, microfragmented anisotropic xanthan/protein complex
dispersion comprising from about 1 to about 50 weight percent of an
insolubilized, hydrated, microfragmented anisotropic xanthan/protein
discontinuous phase dispersed throughout a continuous aqueous phase, said
discontinuous microfragmented xanthan/protein complex phase comprising
irregularly shaped microfragments of an anisotropic hydrated complex
having a xanthan to protein weight ratio in the range of from about 2:1 to
about 1:15, said xanthan/protein microfragments having a particle size
distribution such that substantially all of said microfragments have a
maximum dimension of less than about 15 microns.
31. A microfragmented anisotropic xanthan/protein complex dispersion in
accordance with claim 30 wherein said complex is a molecularly intimate
interaction product of said xanthan and said protein.
32. A microfragmented anisotropic xanthan/protein complex dispersion in
accordance with claim 30 wherein at least about 90 percent by weight of
hydrated microfragments of the aqueous dispersion have a volume of less
than 5.times.10.sup.10 cubic centimeters and have a maximum linear
dimension of about 7 microns.
33. A microfragmented anisotropic xanthan/protein complex dispersion in
accordance with claim 30 comprising microfragments having a mean maximum
dimension in the range of from about 2 to about 10 microns.
34. A microfragmented anisotropic xanthan/protein complex dispersion in
accordance with claim 30 wherein said xanthan/protein complex is a whey
protein complex.
35. A microfragmented anisotropic xanthan/protein complex dispersion in
accordance with claim 30 wherein said xanthan/protein complex is a
xanthan/egg albumen complex.
36. A method in accordance with claim 30 wherein said xanthan/protein
fibers are heated to stabilize substantially all of said xanthan/protein
complex.
37. A frozen dessert composition comprising from about 0 to about 10
percent edible fat, from about 1 to about 10 percent microfragmented
xanthan/protein complex dispersion like that of claim 30, from about 1 to
about 9 percent by weight of protein, from about 10 to about 30 percent by
weight of a saccharide component, and from about 45 percent to about 85
percent water in homogenized, frozen form.
38. A frozen dessert composition in accordance with claim 37 wherein said
fat component comprises from about 2 to about 5 weight percent fat frozen
dessert composition.
39. A food dressing comprising from about 0.25 to about 30 percent by
weight of a microfragmented xanthan/protein complex dispersion like that
of claim 30, from about 0 to about 50 percent by weight of edible oil or
fat, from about 20 to about 96 percent by weight water.
40. An aqueous, microfragmented anisotropic carboxymethyl cellulose/protein
complex dispersion comprising from about 1 to about 50 weight percent of
an insolubilized, hydrated, microfragmented anisotropic carboxymethyl
cellulose/protein discontinuous phase dispersed throughout a continuous
aqueous phase, said discontinuous microfragmented carboxymethyl
cellulose/protein complex phase comprising irregularly shaped
microfragments of an anisotropic hydrated complex having a carboxymethyl
cellulose to protein weight ratio in the range of from about 2:1 to about
1:15, said carboxymethyl cellulose/protein microfragments having a
particle size distribution such that substantially all of said
microfragments have a maximum dimension of less than about 15 microns, and
wherein at least about 90 percent by weight of hydrated microfragments of
the aqueous dispersion have a volume of less than 5.times.10.sup.10 cubic
centimeters and have a maximum linear dimension of less than about 7
microns.
41. A microfragmented anisotropic carboxymethyl cellulose/protein complex
dispersion in accordance with claim 20 comprising microfragments having a
mean maximum dimension in the range of from about 2 to about 10 microns.
42. A frozen dessert composition comprising from about 10 percent edible
fat, from about 1 to about 10 percent microfragmented carboxymethyl
cellulose/protein complex dispersion or carrageenan/protein complex
dispersion, from about 1 to about 9 percent by weight of protein, from
about 10 to about 30 percent by weight of a saccharide component, and from
about 45 percent to about 85 percent water.
43. A frozen dessert composition in accordance with claim 42 wherein said
fat component comprises from about 2 to about 5 weight percent fat frozen
dessert composition.
44. A food dressing comprising from about 0.25 to about 30 percent by
weight of a microfragmented carboxymethyl cellulose/protein complex
dispersion or carrageenan/protein complex dispersion, from about 0 to
about 50 percent by weight of edible oil or fat, and from about 20 to
about 96 percent by weight water.
45. A food dressing comprising from about 0.25 to about 30 percent by
weight of a microfragmented ionic polysaccharide/protein complex
dispersion like that of claim 42, from about 0 to about 50 percent by
weight of edible oil or fat, and from about 20 to about 96 percent by
weight water.
46. A microfragmented ionic polysaccharide/protein complex dispersion in
accordance with claim 23 wherein said microfragments are coated, at least
in part, with calcium alginate or a calcium pectinate.
47. A microfragmented ionic polysaccharide/protein complex dispersion in
accordance with claim 23 wherein said microfragments are coated with
stearoyl lactylate, mono- or diglycerides, lecithin, ionic gum, neutral
gum or mixtures thereof for reducing astringency.
48. A method in accordance with claim 1 further comprising the step of
combining said xanthan/protein complex microfragments in aqueous
dispersion with from about 5 to about 20 weight percent of ionic or
neutral gum or mixtures thereof, based on the total solids weight of said
xanthan/protein complex microfragments.
49. A method in accordance with claim 48 wherein said gum or gum mixtures
are xanthan gum, carboxymethyl cellulose, carrageenan, alginate, locust
bean gum, guar gum and mixtures thereof.
50. A method in accordance with claim 6 further comprising the step of
combining said ionic polysaccharide/protein complex microfragments in
aqueous dispersion with from about 5 to about 20 weight percent of ionic
or neutral gum or mixtures thereof, based on the total solids weight of
said ionic polysaccharide/protein complex microfragments.
51. A method in accordance with claim 50 wherein said gum or gum mixtures
are xanthan gum, carboxymethyl cellulose, carrageenan, alginate, locust
bean gum, guar gum and mixtures thereof.
52. A method in accordance with claim 6 wherein said conducting of said
complex suspension through a zone of high shear to fragment the complex is
carried out by conducting the complex suspension through a very short high
pressure to velocity conversion zone having a length of less than about 2
millimeters with a pressure drop across said conversion zone of at least
about 10,000 psi, and impacting said complex suspension, after passage
through said conversion zone, against a hard surface positioned at a
distance of less than about 4 millimeters downstream from said conversion
zone.
53. A method in accordance with claim 52 wherein the velocity of said
complex suspension at said zone of highest velocity is at least about 1000
feet per second and wherein said zone of highest velocity is provided by a
cylindrical knife edge homogenizer head forming a cylindrical pressure to
velocity conversion zone less than about 1 millimeters in length along the
flow-direction, surrounded by a cylindrical impact ring spaced less than
about 3 millimeters from said cylindrical pressure to velocity Conversion
zone.
54. A processed comminuted meat product comprising from about 5 to about 16
weight percent of meat or vegetable protein, from about 0 to about 25
weight percent animal or vegetable fat, from about 2 to about 30 weight
percent of a microfragmented ionic polysaccharide/protein complex, and
from about 35 to about 75 weiqht percent water, based on the total weight
of said comminuted meat product.
55. A baked sweet dough product having reduced shortening content,
comprising a product baked from a sweet dough comprising from about 15 to
about 60 percent flour, from about 1 to about 3 percent yeast, from about
10 to about 15 to about 40 percent water, from a bout 3.5 to about 15
percent of a sugar, or mixture of sugars, and from about 1 to about 10
percent by weight of a microfragmented ionic polysaccharide/protein
complex dispersion, less than about 5 weight percent of triglycerides, and
having a water activity of greater than 0.9.
Description
BACKGROUND OF THE INVENTION
The present invention is directed to insolubilized, microfragmented ionic
polysaccharide/protein complex aqueous dispersions suitable for
utilization as nutritious bulking, viscosity or texture control agents in
both conventional and novel food products. The microfragmented ionic
polysaccharide/protein complex dispersions, have desirable rheological
properties including a stable lubricity and creamy mouthfeel which may be
utilized in a wide variety of novel, as well as otherwise conventional
food products. The microfragmented xanthan/protein complex dispersions
may, for example, serve as a fat or oil substitute in food products such
as frozen desserts, spreads, dressings, baked goods and sauces. The
present invention is also directed to methods for preparing such
microfragmented anisotropic xanthan/protein complex dispersion
compositions and food products comprising such dispersions.
Substantial technical effort has been directed to the development of oil
replacement compositions which possess a smooth or oily mouthfeel, texture
and lubricity, for use as a full or partial replacement for edible
triglycerides in food products such as margarine, salad dressings such as
mayonnaise, and desserts such as toppings, aerated desserts and ice cream,
which have reduced calorie content. In this regard, synthetic fatty esters
such as sucrose polyesters and polyglycerol polyesters such as described
in U.S. Pat. Nos. 3,353,966 and 3,600,186 have been proposed as
undigestible fat substitutes for various food products.
Significant research effort has also been directed to the study of
complexes of proteins with other polymeric components including various
polysaccharides. For example, alginates have been complexed with proteins
including casein, edestin, yeast protein, gelatin and soy protein.
Gelatin, bovine serum albumen, lysozyme and soy proteins have been
complexed with sodium dextran sulfate, sunflower seed albumen has been
complexed with alginate or pectin, and whey protein has been recovered
from whey through the use of various hydrocolloids. Soybean whey-gum
fibers are also known, and it is known that certain proteins will form
fibers in the presence of specific polysaccharides, as disclosed in U.S.
Pat. No. 3,792,175. As disclosed in the above referred to U.S. Pat. Nos.
4,559,233 and 4,563,360, meat simulating fibers may be prepared from
xanthan gum complexed under appropriate conditions with solubilized
proteins. It would be desirable to provide food products utilizing such
xanthan/protein complexes having a smooth, creamy texture and mouthfeel
for utilization in a wide variety of food products as a full or partial
fat replacement. It would also be desirable to provide methods for
preparing xanthan/protein complex compositions having a smooth, creamy
mouthfeel together with high thermal and dispersion stability, which are
capable of imparting oil-like or creamy organoleptic properties to
specific food products incorporating such xanthan/protein complex
products.
As described in the previously identified U.S. Pat. Nos. 4,563,360 and
4,559,233, xanthan/protein fibrous complexes having desirable
characteristics may be provided by solution coprecipitation techniques.
However, xanthan gum is relatively expensive and may have limited
efficiency for complexing certain protein materials. Accordingly, other
fibrous protein complexes of high food quality utilizing less expensive
and/or more efficient components would be desirable, and the present
invention is also directed to methods for preparing stable, edible,
fibrous polysaccharide/protein complexes in addition to fibrous
xanthan/protein complexes which may be utilized in a wide variety of food
products. In this regard, while xanthan/protein complexes have certain
desirable properties, edible polysaccharide complexes which provide a
further range of characteristics, would also be desirable, as would
complexes which may have improved economics of manufacture through use of
a less expensive or more efficient ionic polysaccharide component in the
provision of stable, aqueous microfragmented dispersions having a stable
lubricity and smooth, creamy mouthfeel. It would be desirable to provide
such dispersions which may, for example, serve as a fat or oil substitute
in food products such as frozen desserts, spreads, dressings, baked goods
and sauces.
It is an object of the present invention to provide methods for the
manufacture of novel, nutritious, low calorie food compositions which have
desirable, smooth, oil-like texture and mouthfeel characteristics, as well
as desirable stability and functionality characteristics. It is a further
object to provide novel food compositions which utilize such complex
dispersions. These and other objects of the invention will become apparent
from the following detailed description and the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram illustrating a specific embodiment of a
continuous method for manufacture of xanthan/protein complex aqueous
dispersion, by continuously forming relatively large fibers, fragmenting
the fibers under high shear conditions to form a microfragmented
dispersion, and concentrating the resulting microfragmented dispersion;
FIG. 2 is a schematic diagram illustrating a specific embodiment of a
method for manufacture of xanthan/protein complex microfragment
dispersions in which the xanthan and protein components are combined under
conditions of high specific turbulent dissipation rate;
FIG. 3a is a photomicrograph, by transmission electron microscopy, of an
insolubilized xanthan/protein fibrous complex prior to microfragmentation
at a magnification of 13,000;
FIG. 3b is a photomicrograph, by transmission electron microscopy, of the
insolubilized anisotropic xanthan/protein complex of FIG. 3a after
microfragmentation, also at a magnification of 13,000;
FIG. 4a is a photomicrograph by scanning electron microscopy of the largest
fragments of the insolubilized xanthan/protein fibrous complex of FIG. 3a
after one pass through a high shear zone at a high specific turbulent
energy dissipation rate, at a magnification of 11,000;
FIG. 4b is a photomicrograph by scanning electron microscopy of the largest
fragments of the insolubilized anisotropic xanthan/protein complex of FIG.
4a after 5 passes through a high shear zone having a high specific
turbulent energy dissipation rate, at a magnification of 22,500;
FIG. 4c is a photomicrograph by scanning electron microscopy of the largest
fragments of the insolubilized anisotropic xanthan/protein complex of FIG.
4a after 5 passes through a high shear zone having a high specific
turbulent energy dissipation rate, at a magnification of 11,000;
FIG. 5a is a photomicrograph by scanning electron microscopy of a fiber
fragment of a fully denatured xanthan/protein fibrous complex after low
intensity homogenization treatment, at a magnification of 1125;
FIG. 5b is a photomicrograph by scanning electron microscopy of the fiber
fragment of the insolubilized anisotropic xanthan/protein complex of FIG.
5a, at a magnification of 11,000;
FIG. 5c is a photomicrograph by scanning electron microscopy of the
microfragment dispersion produced by high shear treatment of the fiber
fragment produced by FIGS. 5a and 5b, at a magnification of 11,000;
FIG. 6 is a graphical representation of a differential scanning calorimetry
analysis of an embodiment of an anisotropic partially denatured
microfragmented xanthan/protein complex;
FIG. 7 is a graphical representation of a differential scanning calorimetry
analysis of an anisotropic, substantially fully denatured microfragmented
xanthan/protein complex;
FIG. 8 is a graphical representation of a differential scanning calorimetry
analysis of a protein emulsion prepared without xanthan gum;
FIG. 9 is a photomicrograph of a microfragmented, anisotropic
xanthan/protein complex dispersion at pH 5.5, by scanning electron
microscope at a magnification of 1000;
FIG. 10 is a photomicrograph of the xanthan/protein complex dispersion of
FIG. 9 at a pH of 4.0 at a magnification of 1000;
FIG. 11 is a graphical representation of the turbidity remaining after
centrifugation at 1600.times.g for 10 minutes at room temperature, of a
microfragmented xanthan/protein complex aqueous dispersion of FIGS. 9 and
10 at 100 fold dilution as a function of dispersion pH, for various levels
of salt content;
FIG. 12 is a graphical representation of the turbidity remaining after
centrifugation at 1600.times.g for 10 minutes at room temperature, of the
microfragmented xanthan/protein complex dispersion of FIG. 9 and 10 at 100
fold dilution as a function of sodium chloride concentration for
dispersions of different pH;
FIG. 13 is a graphical representation of the Haake viscosity of another
embodiment of a partially denatured microfragmented xanthan/protein
complex dispersion both before and after the heat treatment of the
dispersion at its boiling point;
FIG. 14 is a schematic diagram illustrating a specific embodiment of a
continuous method for manufacture of xanthan/protein complex
microdispersions in which the solubilized xanthan and protein components
are continuously conducted through a zone of high specific turbulent
dissipation rate under complex forming conditions;
FIG. 15 is a schematic diagram illustrating a specific embodiment of a
batch-type method for manufacture of xanthan/protein complex
microdispersions in which the solubilized xanthan and protein components
are conducted through a zone of high specific turbulent dissipation rate
as complex forming conditions are developed in the batch undergoing
processing;
FIG. 16 is a graphical illustration of electrophoretic/pH relationship of a
xanthan/egg white-whey protein concentrate gel formed at a 1:1:1 solution
weight ratio, as compared to a xanthan/egg white-whey protein concentrate
fiber complex formed at a 1:4:4 weight ratio;
FIG. 17 is a schematic illustration of a process for preparation of
carboxymethyl cellulose/protein and lambda carrageenan/protein fibers;
FIG. 18 is a schematic diagram of methods for removing undesirable flavor
components from polysaccharide protein complex forming solutions;
FIG. 19 is an illustration of a gas atomization system for preparation of a
microparticulate polysaccharide/protein complex dispersion;
FIG. 20 is a schematic illustration, partially broken away, and with
enlarged inserts, of a gas atomization nozzle and a large particle filter
assembly for preparation by atomization of an aqueous ionic
polysaccharide/protein complex dispersion;
FIG. 21 is a graphic illustration of electrophoretic mobility/pH
relationships of carboxymethyl cellulose/protein complex and starting
ingredients, with a mobility unit of 10E-8 meter/sec/volt meter;
FIG. 22 is a light micrograph of boiled carboxymethyl cellulose/egg
white/whey protein complex fibers (30.times. magnification);
FIG. 23 is a graphic illustration of electrophoretic mobility/pH
relationships of microfragmented xanthan/egg white+whey protein and
carboxymethyl cellulose/egg white+whey protein complexes, respectively,
with a mobility unit of 10E-8 meter/sec/volt meter;
FIG. 24 is a light micrograph of carboxymethyl cellulose/protein complex
fragments dispersed in sodium cacodylate buffer, at a magnification of 800
showing particles ranging in size from approximately 0.5 to 5 microns;
FIG. 25 is a scanning electron micrograph of carboxymethyl
cellulose/protein complex fragments at a total magnification of 25,000;
FIG. 26 is a transmission electron micrograph of carboxymethyl
cellulose/protein complex fragments at a magnification of 8,000;
FIG. 27 is a graphic representation of viscosity vs. concentration for an
aqueous carboxymethyl cellulose/protein complex dispersion, and a
xanthan/protein comparison sample;
FIG. 28 is a graphic representation of viscosity vs. pH for an aqueous
carboxymethyl cellulose/protein complex dispersion at weight percent
levels of 5 and 13 percent, respectively;
FIG. 29 is a graphic representation of the effect of added sodium chloride
on the viscosity of xanthan/protein and carboxymethyl cellulose/protein
complex dispersions;
FIG. 30 is a graphical representation of the turbidity of a
chitosan/protein complex supernate;
FIG. 31 is a graphical representation of the protein concentration of the
chitosan/protein complex of FIG. 30;
FIG. 32 is a graphical representation of the relationship of
electrophoretic mobility of a chitosan/egg white/whey protein complex as a
function of PH, together with the respective mobilities of the individual
components;
FIG. 33 is a scanning electron photomicrograph of a microfragmented
chitosan/protein complex at a magnification of 10,000;
FIG. 34 is a scanning electron photomicrograph of a microfragmented
carboxymethyl cellulose protein complex at a magnification of 10,000;
FIG. 35 is a scanning electron photomicrograph of a microfragmented
carrageenan protein complex at a magnification of 11,000;
FIG. 36 is a graphical representation of the relationship of
electrophoretic mobility of a carrageenan/egg white/whey protein complex
as a function of pH, together with the respective mobilities of the
individual components;
FIG. 37 is a scanning electron photomicrograph of a microfragmented
gellan/xanthan protein complex at a magnification of 10,000;
FIG. 38 is a graphical representation of the relationship of
electrophoretic mobility of a gellan/egg white/whey protein complex as a
function of pH, together with the respective mobilities of the individual
components;
FIGS. 39a, 39b and 39c are flow curves of aqueous CMC/protein complex
dispersions under various conditions of complex concentration, pH and
added salt concentration;
FIG. 40 is a photomicrograph of a reduced fat (50%) model mayonnaise
emulsion containing a microfragmented xanthan/protein fiber complex
dispersion at a magnification of 10,500.times.; and
FIG. 41 is a photomicrograph of a reduced fat (50%) model mayonnaise
emulsion containing a microfragmented xanthan/protein gel complex
dispersion at a magnification of 10,500.times..
DESCRIPTION OF THE INVENTION
The present invention is directed to the provision of aqueous dispersions
of insolubilized, microfragmented polysaccharide/protein complexes which
are useful as a nutritious bulking, viscosity or texture control agent and
having desirable rheological characteristics of stable lubricity and
creamy mouthfeel. Such aqueous, microfragmented polysaccharide/protein
complex dispersions may comprise from about 1 to about 50, and typically
from about 2 to about 25 weight percent of an insolubilized, hydrated,
microfragmented ionic polysaccharide/protein complex discontinuous phase
dispersed throughout a continuous aqueous phase, the discontinuous
microfragmented ionic polysaccharide/protein complex phase comprising
irregularly shaped microfragments of a hydrated complex having an ionic
polysaccharide to protein weight ratio in the range of from about 2:1 to
about 1:20, with the ionic polysaccharide/protein microfragments having a
particle size distribution such that substantially all of said
microfragments have a maximum dimension of less than about 15 microns. The
microfragmented ionic polysaccharide/protein complex dispersions are
preferably of a syneresed, molecularly intimately entangled interaction
product of an ionic polysaccharide and a protein. Desirably, at least
about 90 percent by weight of hydrated microfragments of the aqueous
dispersion have a volume of less than 5.times.10.sup.-10 cubic centimeters
and have a maximum linear dimension in the range of from about 2 to about
10 microns and preferably less than about 7 microns.
Methods for producing such microfragmented ionic polysaccharide/protein
dispersions are provided comprising the steps of forming an aqueous
suspension of a syneresed molecularly intimately entangled complexed ionic
polysaccharide/protein complex precipitate, conducting said syneresed
complex suspension through a zone of high shear to fragment the complex
under sufficient conditions cf shear and duration to reduce substantially
all of said complex to ionic polysaccharide/protein complex microfragments
having a maximum dimension of less than about 15 microns. The high shear
zone should best have a shear rate of at least about 37,000 inverse
seconds , with a turbulent energy dissipation rate sufficient to raise the
temperature of the suspension at least about 5.degree. C. through viscous
dissipation of input energy to heat. Substantially higher shear rates may
be appropriate for various complexes. The complexed precipitate which is
conducted through the high shear zone, as will be described in more detail
hereinafter, desirably comprises at least about 5 and more preferably at
least about 8 weight percent of ionic polysaccharide and at least about
20, preferably at least about 25, and more preferably for certain uses, at
least about 50 weight percent of protein, based on the total (dry) solids
weight of the complexed, syneresed precipitate.
The polysaccharide component may desirably be an edible anionic
polysaccharide such as polysaccharides having pendant carboxylic acid
groups, and polysaccharides having pendant sulfate groups. Examples of
edible polysaccharides having pendant carboxylic acid groups include water
soluble carboxymethyl cellulose, pectins, algin and alginates, and
microbial gums such as gellan, as well as xanthan gum. Examples of edible
polysaccharides having pendant sulfate groups include iota, kappa and
lambda carrageenan, and various agaroid gums and gum components.
The polysaccharide may also be a cationic polysaccharide. An example of a
cationic polysaccharide includes chitosan, which is a polyaminoglucose
derived from natural chitin.
Various precipitated polysaccharide/protein complexes, which may or may not
initially be in the form of large fibers, may be subjected to conditions
of intense shear, to fragment the solid, complex particles (e.g., small
fibers, curd-like pieces, etc.) to produce an aqueous dispersion having
smooth, creamy characteristics. Such polysaccharide/protein complexes are
desirably, but not necessarily, heat denatured, syneresed, reticulated
polysaccharide complexes. In this regard, by "heat-denatured" is meant the
loss of the native secondary and tertiary protein structure through the
effect of heat. By "syneresed" is meant that the polysaccharide/protein
complex components are formed by expulsion of water by molecularly
intimately entangled polysaccharide and protein components which are
ionically complexed in a network having a solids density of at least about
10 weight percent total solids at 25.degree. C. at the isoelectric point
pH of the complex. Desirably, the complexes may have an intermolecular
ionic bond energy between the ionic polysaccharide and the protein
components of at least about 0.25 and more desirably at least about 0.5
calories per gram of the complex (dry basis), at the isoelectric point pH
of the complex, under conditions of substantially complete ionic bond
formation. Upon heating, the stability of the entanglement of the ionic
polysaccharide with protein component may be further influenced by
additional interactive bonding effects. By "reticulated" is meant that the
molecularly intimate complex of protein and polysaccharide is formed in a
network structure which is observable at a magnification of 10,000, and
will desirably have a wide volume of at least 10 volume percent in which
the complex is absent.
Such solid polysaccharide/protein complexes may be formed from an
appropriate complex forming solution comprising a suitable, solubilized
polysaccharide component and a solubilized protein component, by adjusting
the pH to precipitate a polysaccharide/protein complex.
By appropriate selection of the ionic polysaccharide component and the
protein component and the interaction conditions, a wide variety of
syneresed ionic polysaccharide/protein complex precipitation may be
provided ranging from substantially isotropic gels to fibrous anisotropic
products, as will be described in detail.
The aqueous complex generating solution will include vegetable or animal
proteins, or mixtures thereof. Such a complex generation solution may, for
example, comprise a solubilized edible protein polymer component such as
soy protein (particularly including soy protein isolate), casein, egg
protein, peanut protein (particularly including peanut protein isolate),
cottonseed protein (particularly including cottonseed protein isolate),
sunflower protein (particularly including sunflower protein isolate), pea
protein (particularly including pea protein isolate), whey protein, fish
protein, crustacean protein and other seafood protein, animal protein and
mixtures thereof. Cereal and grain proteins alone or in combination with
other cereal, grain or other proteins, which may be solubilized in water,
are useful protein components. In this regard, the water soluble proteins
(albumens), salt soluble proteins (globulins), alcohol soluble proteins
(prolamins and gliadins) and acid and alkali soluble proteins (glutelins)
of cereals and grains such as corn, barley, wheat, buckwheat and oats are
contemplated herein as protein sources. For example, zein, the prolamin
protein of corn, may be readily obtained by dissolution in aqueous alcohol
from corn gluten, and becomes soluble in dilute aqueous alkali (e.g., 0.02
to 0.2 normal NaOH). The various protein components may be utilized to
produce aqueous microfragment dispersions of varied properties. For
example, polysaccharide complexes with egg albumen readily denature at
elevated temperature to stabilize the complex. The high proportion of
nonpolar and acid amide side chains of prolamins such as zein may be
utilized alone or with other proteins in forming polysaccharide complexes,
to provide aqueous dispersions of varied, useful properties. One or more
of these aqueous solubilized undenatured protein components may desirably
comprise at least about 50 weight percent of the solubilized proteins,
based on the total weight of the solubilized protein, for preparing
microfragmented complex dispersions for a variety of uses. Gelatin may
also be included in amounts (e.g., 20 weight percent based on the total
dry weight of the protein component) which do not prevent fiber formation
(when fiber formation is desired), particularly when it is desired to
minimize the presence of sulfhydryl groups on the surface of the
microfragments. Fish and shellfish proteins and single cell proteins are
also contemplated. Egg white protein, casein (e.g., as sodium caseinate),
soy protein isolate and mixtures of soy protein isolate and egg albumen
are particularly preferred edible protein polymer components. Whey protein
is a readily available protein which may be used alone or in combination
with other proteins.
A particularly preferred protein component for preparing bland, high
quality microfragmented complex aqueous dispersions is a mixture of skim
milk and egg white protein. The skim milk and/or egg white proteins may be
diafiltered or concentrated such as by methods such as ultrafiltration.
Typically, the weight ratio of skim milk protein to egg white protein will
be in the range of from about 4:1 to about 1:4, on a solids basis.
By "solubilized protein" is meant a protein that is hydrated by existing
either in true solution (single phase) or in a stabilized dispersion which
upon initial dispersion in water may appear to be a single phase but after
a period of time may separate into two phases. By "solubilized undenatured
protein" is meant a solubilized protein having its natural secondary and
tertiary structure substantially intact. The solubilized undenatured
edible protein component will desirably have an isoelectric point(s)
greater than about 3, preferably in the range of from about 4 to about 10.
Particularly useful proteins may have an isoelectric point in the range of
from about 4 to about 7. In this regard, typically soy protein isolate may
have an isoelectric point of about 4.5, egg albumen of about 4.7 and
casein of about 4.5. It is noted that various constituents of the
solubilized edible protein component may have different isoelectric
points. However, it is important that the various protein components when
complexed with the ionic polysaccharide component may form fibrous or
gel-like complex precipitates at a preselected reaction pH which is
determined by the isoelectric point of the fibrous complex. In this
regard, particularly preferred compositions in accordance with the present
invention include multiple protein complex fibers such as fibers of
xanthan gum complexed with skim milk protein together with egg white
protein. Very bland casein, whey protein or soy protein, may also be used
together with egg albumen.
A protein is desirably solubilized at a pH of at least about 1 pH unit from
its isoelectric point, and preferably at 2 pH units or greater from its
isoelectric point. The complex generating solution further includes an
ionic polysaccharide component which will be described in more detail.
The polysaccharide/protein complex may be formed by adjusting the pH of a
solution of the dissolved protein and polysaccharide components to a pH at
which the complex precipitates, without necessarily forming a fibrous
precipitate.
A wide variety of complexes may be prepared, having a variety of unique
specific characteristics which are desirable or essential to specific
uses. For example, fibrous anisotropic xanthan/protein complexes such as
xanthan/skim milk-egg white complexes have specific rheological food
product compatibility, mouthfeel and bland flavor properties which are
particularly desirable for food products such as frozen desserts and salad
dressings. Carrageenan-, CMC (carboxymethyl cellulose)-, chitosan-, and
gellan- egg white/whey protein complexes may be designed and prepared
which have high protein utilization efficiencies and other respectively
desirable properties, by adjusting the pH of dissolved
polysaccharide/protein mixtures near the isoelectric points of the
complexes, as determined by electrokinetic analysis. Although the various
types of complexes are described herein as having certain common end uses
or methods of preparation, they are not regarded as equivalent materials
in view of the different characteristics which may be provided.
The complex forming solution may also include water solubilized,
substantially nonionic edible polysaccharides such as dissolved starch,
solubilized agar and agaroids, dissolved guar gum, dissolved carob gum,
water soluble dextrans, water or alkali soluble edible grain bran and/or
hemicellulose constituents such as solubilized wheat gum, solubilized
wheat bran, solubilized oat bran and solubilized corn bran constituents,
as well as mixtures of such nonionic polysaccharides. Such nonionic
polysaccharide components, which may be dissolved in the complex forming
solution together with the ionic polysaccharide and protein polymer
components, may become entangled and enmeshed with the ionic
polysaccharide/protein complex which is formed upon pH adjustment of the
complex forming solution. The nonionic polysaccharide component may
typically tend to increase the water content of the polysaccharide/protein
complex. It is desirable that the hydrated complex itself contain at least
about 10 weight percent of solids, and preferably for a variety of uses,
at least about 15 weight percent solids, and preferably from about 20 to
about 40 weight percent solids. For example, when an ionic
polysaccharide/protein complex having 40 weight percent solids is
dispersed as microfragments in an equal weight of water, a 20 weight
percent solids dispersion is prepared which has a total solid content of
20 weight percent and a thick consistency resulting from its limited 50
weight percent continuous aqueous phase. The amount and type of nonionic
polysaccharide may be adjusted to provide a desired solids level for a
particular complex.
Starch may be included in relatively high quantities, while high viscosity
water retaining materials such as agar may best be included in relatively
small amounts, such as from about 0.1 to about 2 percent based on the
total weight (dry basis) of the complex.
Solubilized starch is a particularly desirable nonionic polysaccharide
component in view of its relatively bland taste, relatively low caloric
content when hydrated, and its price-performance effectiveness. Starch may
desirably be included in the complex forming solutions, and in the
precipitated complexes, in amounts of from about 1% to about 75% by
weight, based on the total weight of the polysaccharide/protein complex on
a dry basis. For various uses, the starch will preferably be included in
the precipitated complexes in an amount in the range of from about 10
percent to about 50 percent by weight, based on the total weight of the
complex on a dry basis.
Starch components may include amylose, amylopectin and mixtures thereof.
Useful starch components, include corn starch, potato starch and tapioca
starch. Amylopectin and high amylopectin starches such as waxy maize
starch and waxy milo starch may be dissolved or fully gelatinized and
introduced into the fiber generating solution prior to pH adjustment for
complex formation, to provide high molecular weight starch components
which entangle readily with the other components upon precipitation. Fully
gelatinized amylose and high amylose starch sources such as obtained from
high amylose corn varieties containing at least 75% by weight amylose
based on the total starch content, may also be utilized. Such amylose has
a linear structure which is subject to retrogradation. The linear amylose
molecules can interact and associate with one another to contribute to the
interlacing network extending through the xanthan/protein complex, and
contribute to the syneresis of water from the complex. Corn starch, which
is a mixture of amylose and amylopectin, may be desirably included in the
fiber forming solution in amounts ranging up to about three times the
total weight of the ionic polysaccharide components, although from about
0.25 to about 2 times the weight of the ionic polysaccharide weight is a
preferred range.
As indicated, such nonionic polysaccharide components should best be
solubilized in the complex forming solution, and in this regard,
polysaccharides such as starches which require elevated temperatures for
dissolution should best be dissolved in water at elevated temperature and
at least partially cooled below the respective denaturation temperature
before mixing with any undenatured protein components. The ionic
polysaccharide, however, may be dissolved with the starch at elevated
temperature, and will tend to prevent gel formation or retrogradation upon
cooling. The nonionic polysaccharide solution of the ionic polysaccharide
and nonionic polysaccharide solution should best be mixed with the protein
component at a temperature below a temperature at which any substantial
portion of the protein is denatured. In this manner, the dissolved starch
or other nonionic polysaccharide, the protein and the ionic polysaccharide
may be fully intermixed in solution prior to pH adjustment to form the
polysaccharide/protein complex. It is noted that microfragmentation of
various undissolved polysaccharide materials with the formed complex may,
however, serve to provide an aqueous dispersion having a desirable smooth,
creamy texture in which the undissolved polysaccharide materials are
fragmented into particles having a major dimension less than, for example,
10 microns in length.
The weight ratio of ionic polysaccharide to solubilized protein in the
complex forming solution will generally be in the range of from about 1:2
to about 1:15, and preferably from about 1:4 to about 1:10. The preferred
weight ratios of the precipitated complexes will generally be in the same
ranges, although as described hereinafter, the ratio of ionic
polysaccharide to protein may be substantially greater in the complex
precipitate than in the solution, if protein recovery is not complete.
The total solids content of the complex forming solution will best be in
the range of from about 1 to about 30 weight percent, and preferably in
the range of from about 1.5 to about 10 percent by weight (typically about
2-3 percent by weight), based on the total weight of the complex forming
solution.
The precipitated polysaccharide-protein complexes may be stabilized by
boiling or other high temperature denaturation treatment. Any off-flavor
components associated with the complexes may be removed by washing. Such
boiled and washed polysaccharide-protein complexes may be microfragmented
by subjecting an aqueous slurry or suspension of the complex to intense
shear to provide microfragmentation treatment. Effective results have been
achieved by using a CD150 or a MC15 cell disruptor using a knife edge
homogenization element within a closely surrounding impact ring (A.P.Z.
Gaulin Corp., Boston, Mass.) at an inlet pressure of at least about 3000
psig and preferably at least 10,000 psig to obtain microfragments smaller
than fifteen microns preferably smaller than 5 microns in maximum
dimension. The dispersion may be passed through a cell disruptor or other
high shear zone, a sufficient number of times to provide a desired
particle size. The microfragmented dispersion will desirably have a total
solids content of the ionic polysaccharide/protein complex particles in
the range of from about 1 to about 30 percent and typically from about 1
to about 10 percent, by weight, solids basis, based on the total weight of
the aqueous dispersion. Microfragmentation of dispersions over about 10
weight percent solids content may be difficult. If a low solids content
dispersion is formed by high pressure shearing, the resulting dispersion
may be concentrated by ultrafiltration, thin film evaporation or
centrifugation procedures, if desired. After concentration, these
microfragmented polysaccharide/protein complexes are found to be smooth,
creamy, bland, white, and have a fat-like mouthfeel, and can be used as a
fat replacer in a variety of food products. For example, mayonnaise
products prepared with 50 weight percent of the oil replaced by these
microfragmented polysaccharide/protein complexes are stable, smooth, and
creamy.
Insolubilized, microfragmented, anisotropic xanthan/protein complex
dispersions are preferred compositions having a creamy mouthfeel, as well
as specific desirable stability, functional and other characteristics,
which may be utilized in various food products. For example, such
microfragmented xanthan/protein complex dispersions may function as low
calorie, nutritious, full or partial oil or fat replacements in a variety
of food products such as frozen desserts, spreads, dips, dressings,
sauces, processed and analog cheese products, cultured dairy products,
processed meat products such as hot dogs and luncheon meats and baked
goods. Such microfragmented xanthan/protein complex dispersions may also
contribute desirable mouthfeel, moisture control, texture, stabilizing,
enrichment, hydrating and bulking properties under a broad range of
conditions for a wide range of food applications.
Microfragmented anisotropic xanthan/protein complex dispersions in
accordance with the present invention may typically comprise from about 1
to about 50 weight percent of an insolubilized, hydrated microfragmented
anisotropic xanthan/protein complex discontinuous phase dispersed
throughout a continuous aqueous phase, based on the total solids content
of the xanthan/protein complex in the dispersion. In particularly
preferred embodiments, the discontinuous anisotropic xanthan/protein
complex phase will generally comprise irregularly shaped microfragments of
an anisotropic, hydrated xanthan/protein complex having a particle size
distribution, such that substantially all of the xanthan/protein complex
microfragments of the dispersion have a maximum dimension of less than
about 15 microns. The anisotropic xanthan/protein complex is a molecularly
intimate interaction product of xanthan and a protein in proportions which
produce a material having physical and functional properties differing
substantially from either the protein component or the xanthan component
alone. Desirably, at least about 90 percent by weight of the hydrated
microfragments of the aqueous dispersion have a volume of less than about
5.times.10.sup.-10 cubic centimeters, and a maximum linear dimension of
less than about 7 microns. Xanthan/protein microfragments having a mean
maximum dimension in the range of from about 2 to about 10 microns provide
desirable, creamy mouthfeel and other properties, although smaller
microfragments may also be utilized. Fibers or other particles larger than
20 microns in length, which may be utilized, for example, for the purpose
of introducing properties such as fibrous or chewy texture in a specific
food product in addition to the creamy texture, are not included in this
calculation of weight percent. The hydrated, molecularly intimately
combined xanthan/protein complex microfragment particles of the aqueous
dispersion will desirably have a xanthan/ protein weight ratio of from
about 2:1 to about 1:20, more preferably in the range of from about 1:2 to
about 1:10. Xanthan/protein complex fiber formation may occur only at an
intermediate range of xanthan/protein ratio, while xanthan/protein complex
gels, which may also be utilized in the preparation of microfragmented
xanthan/protein complex dispersions, may be formed over a relatively wider
or different range of conditions and ratios. At least about 5 weight
percent, and preferably at least 10 weight percent, based on the dry
weight of the xanthan/protein molecularly intimate complex should be the
xanthan gum component, in order to provide substantial properties of the
complex, as compared with the properties of the protein itself. As
indicated, the insolubilized xanthan/protein complex microfragments are
desirably anisotropic, and in this regard, by "anisotropic" is meant that
the insoluble microfragments have irregular particle shapes having a
significant statistical deviation from sphericity.
Such microfragmented anisotropic xanthan/protein dispersions have
particularly desirable shelf-life, thermal, pH and dispersion stability,
and a high functionality to weight percent of solids ratio together with
smooth, creamy texture and mouthfeel characteristics, and a bland taste
which is generally compatible with a wide variety of food products.
The irregularity of the microfragments and their significant departure from
sphericity, together with their bulk and surface properties are believed
to provide a wide degree of stable functionality at a relatively low total
solids content. The high bulk stability of the xanthan/protein complex is
also believed to contribute significant thermal stability and storage
stability in respect to product properties and bland taste to the
microfragment dispersion.
Food products comprising such xanthan/protein complex dispersions may be
provided which have novel and particularly desirable characteristics, as
will be more particularly described hereinafter. Such products may
comprise from about 1 to about 20 percent by weight (solids basis) of the
xanthan/protein complex dispersion, from about 10 to about 90 percent by
weight moisture, from about 0 to about 80 percent carbohydrate, from about
0 to about 35 percent by weight protein (other than the xanthan/protein
complex) and from about 0 to about 50 percent by weight of fat, as well as
salt, flavoring agents and other food components. Various specific food
applications will be described in more detail hereinafter.
The microfragmented anisotropic xanthan/protein complex dispersions may be
prepared by initially forming relatively large xanthan/protein complex
fibers under fiber-forming conditions in which an anisotropic complex is
formed, and subsequently shearing an aqueous slurry of such fibers under
high energy shear conditions to comminute the fibers to smaller
anisotropic fiber microfragments having a maximum dimension of 15 microns
or less. As described in U.S. Pat. Nos. 4,563,360 and 4,559,233,
xanthan/protein complex fibers may be formed from aqueous fiber-generating
solutions of xanthan gum and protein under specific fiber-forming
conditions. It is desirable that the pre-formed xanthan/protein complex
fibers, particularly those fibers prepared from protein sources such as
whey protein concentrate which may contain undesired flavor components, be
washed with water after formation. At least an equal volume of water to
the volume of the fibers should be used, desirably in a countercurrent
process. In this regard, in such methods of microfragmented
xanthan/protein complex dispersion manufacture which utilize an initial
relatively large fiber formation step, it is desirable to separate at
least a portion of the fiber whey solution formed by the fiber generating
solution under fiber formation. The whey separation step not only
increases the concentration of the fibers for subsequent processing, but
may also remove undesirable flavor components which could interfere with
subsequent food product formulation. Desirably, at least about 50 volume
percent and more preferably at least about 75 volume percent of the fiber
whey solution is separated from the fibers. In addition, the
xanthan/protein complex fibers may desirably be washed with at least an
amount of water equal to, and more preferably, at least about two times
the volume of the fibers, before subsequent microfragmentation. It is also
particularly desirable that the xanthan/protein complex fibers be heated
to a temperature sufficient to denature at least about 50 weight percent
of the protein, and more preferably at least about 80 percent of the
protein, prior to microfragmentation. The washing step may desirably be
carried out subsequent to, or concomitantly with the denaturation
stabilization step, for example, by boiling the preformed fibers in a
quantity from the clean wash water.
By "relatively large" or "pre-formed" fibers is meant fibers having a
length of at least about 20 microns Such xanthan/protein complex fibers
may have significant physical integrity, which varies anisotropically,
such that high shear forces are required to tear the fibers into
microfragments, preferentially along zones or surfaces of weaker
integrity, thereby producing irregularly shaped microfragments. The high
shear comminution may be carried out in an aqueous slurry without other
food components. Alternatively, the high shear treatment step may be
carried out with other food product components which are dissolved in the
aqueous phase, or which are also intended to be emulsified or otherwise
thoroughly dispersed in the preparation of the food product containing the
xanthan/protein complex dispersion, as will be described in more detail
hereinafter.
As indicated, high shear microfragmentation in aqueous dispersion may be
utilized to produce anisotropic microfragmented xanthan/protein complex
dispersions in accordance with the present disclosure. Such high shear
treatment may be carried out in any suitable manner, such as by hydroshear
mixers, ultrasonic mixers, and colloid mills, and mixer homogenizers, as
will also be described in more detail. High energy hydroshear mixers such
as described in U.S. Pat. No. 4,533,254 have been demonstrated to be
particularly desirable for xanthan/protein complex microfragment
dispersion formation from preformed xanthan/protein fibers.
In a preferred method of microfragmenting the preformed anisotropic
xanthan/protein complex fibers, an aqueous xanthan/protein fiber slurry is
subjected to high levels of shear rate and kinetic energy dissipation. For
example, a slurry containing from about 4 to about 5 percent by weight of
preformed, relatively large xanthan/protein complex fibers (solids basis)
with a viscosity not exceeding 1000 centipoise may be conducted through a
high shear zone at initial linear velocities of at least about 1000 feet
per second, and more preferably at least about 1300 feet per second, and
then rapidly decelerated to achieve fragmentation of the fibers.
The preformed anisotropic fibers should best be conducted through a high
shear zone having a shear rate of at least about 37,000 seconds.sup.-1 and
preferably at least about 5.times.10.sup.6 (e.g., 1.times.10.sup.7)
seconds.sup.-1 at a specific turbulent energy dissipation rate of at least
about 8.5.times.10.sup.5 ergs per cubic centimeter of the high shear zone.
Preferably, all of the fiber slurry is conducted through the high velocity
and shear fragmentation zone. In a flow through system with continuous
high shear treatment, the specific energy requirement (the energy
dissipation rate per unit throughput of product stream) may desirably be
at least about 1.times.10.sup.8 ergs per gram. Preferably, a turbulent
energy dissipation rate of at least about 4.times.10.sup.11 ergs per pound
of aqueous dispersion is provided per pass through the high shear, high
velocity zone. The kinetic and shearing forces are dissipated and
converted viscously to heat and fragmentation of the complex, and the
temperature of the dispersion may rise at least about 10.degree. C. such
as at least about 30.degree. C. upon conduction through the high velocity
and shear microfragmentation zone. The high shear and rapid deceleration
tears and fragments the larger fibrous xanthan/protein complex fibers into
irregularly shaped microfragments, preferentially along surfaces of
weakness of its fibers.
In methods of microfragmented anisotropic xanthan/protein dispersion
formation utilizing an initial aqueous slurry of preformed anisotropic
fibers, the aqueous slurry will desirably comprise less than about 20 and
preferably in the range of from about 2 to about 10 weight percent of
xanthan/protein fibers (solids basis), in order to provide effective fiber
comminution to the desired irregular particle size distribution. The
preformed fibers to be subjected to subsequent microfragmentation may be
provided from an aqueous protein fiber generating solution of vegetable or
animal proteins, or mixtures thereof, as previously described.
The fiber generating solution further includes a solubilized xanthan gum
hydrocolloid polymer component selected from the group consisting of
xanthan gum, xanthan gum/hydrocolloid adducts and mixtures thereof, as
will be discussed hereinafter, various other polysaccharide components may
be utilized alone, or with xanthan gum, to provide complex dispersions
having a variety of characteristics and properties. Soy protein isolate
and mixtures of soy protein isolate and egg albumen are particularly
preferred edible protein polymer components. For xanthan-protein complex
microfragment dispersion manufacture, it is particularly desirable that
the fiber-forming protein be substantially fully dissolved. Protein such
as egg white protein, whey protein in undenatured condition and mixtures
thereof readily form a true solution in water and are particularly
desirable for microfragment dispersion preparation in accordance with the
present disclosure. The edible protein polymer component will desirably
have an isoelectric point(s) greater than about 3, preferably in the range
of from about 4 to about 10. Particularly useful proteins may have an
isoelectric point in the range of from about 4 to about 7. In this regard,
typically soy protein isolate may have an isoelectric point of about 4.5,
egg albumen of about 4.7, whey protein of about 4.5, and casein of about
4.5. It is noted that various constituents of the solubilized edible
protein component may have different isoelectric points. However, it is
important in the provision of fibers comprising xanthan complexed with a
plurality of proteins that the isoelectric point of the various protein
components, when complexed with the xanthan gum component, form fibrous
precipitates at a preselected reaction pH which is determined by the
isoelectric point of the fibrous complex. In this regard, particularly
preferred compositions in accordance with the present invention include
anisotropic multiple-protein complex fibers such as xanthan/(whey protein
and egg albumen protein) complex fibers, xanthan/(soy protein+egg albumen)
complex fibers, xanthan/(whey protein+soy protein) complex fibers and
xanthan/(whey protein, soy protein and egg protein) complex fibers.
The solubilization of the protein and the xanthan gum under non-fiber
forming conditions is believed to be important to the formation of
molecularly intimate xanthan/protein complexes having properties differing
from the xanthan or the protein components in significant characteristics.
A protein is desirably solubilized at a pH of at least about 1 pH unit
from its isoelectric point, and preferably at least 2 pH units or greater
from its isoelectric point. Such solubilized proteins may preferably
include dairy whey protein, egg albumen protein and vegetable protein
isolates. By "vegetable protein isolate" such as "soy protein isolate" and
"peanut protein isolate" is meant a protein preparation containing at
least about 90% protein.
By "xanthan gum" is meant the heteropolysaccharide produced by fermentation
of the microorganism of the genus Xanthomonas. A discussion of the
physical and chemical properties may be found in Industrial Gums, R. L.
Whistler, Ed., Academic Press, N.Y. (1973), p. 473.
Xanthan gum in aqueous solution with an appropriate counterion such as
sodium or potassium is highly negatively charged because its side chains
are composed of charged glucuronic acid, mannose and its pyruvate
derivative. In aqueous solution, the highly charged mutually repelling and
relatively bulky side chains, which are regularly disposed along the
relatively narrow backbone, are believed to provide hydrated xanthan gum
with a relatively linear structure, which is further believed to be an
important factor in the provision of the desirable properties and
functionality of the molecularly intimate complexes which may be formed
with solubilized protein components, in the preparation of microfragmented
xanthan/protein complex dispersions, and food products containing such
complexes, as will be further discussed.
By xanthan gum adduct is meant a complex of xanthan gum with another
hydrocolloid. Xanthan gum forms adducts with other hydrocolloids such as
carob gum in which it is believed that the extended linear nature of the
xanthan gum in solution is preserved. Desirably, the xanthan gum adducts
should comprise at least about 20 weight percent of xanthan gum, based on
the total weight of the xanthan gum and the adduct component.
The fiber forming solution may also include substantially fully hydrated,
substantially nonionic edible polysaccharides such as fully gelatinized
dissolved starch, solubilized agar and agaroids, dissolved guar gum,
dissolved carob gum (in addition to that which may be complexed with the
xanthan gum component), water soluble dextrans, water or alkali soluble
edible grain bran and/or hemicellulose constituents such as solubilized
wheat gum, solubilized wheat bran, solubilized oat bran and solubilized
corn bran constituents, as well as mixtures of such nonionic
polysaccharides, as previously described. It is desirable that the fibers
themselves contain at least about 15 weight percent of solids, and
preferably for a variety of uses, at least about 20 weight percent solids,
and the amount and type of nonionic polysaccharide may be adjusted to
provide a desired solids level.
Substantially fully hydrated starch is a particularly desirable nonionic
polysaccharide component in view of its relatively bland taste, relatively
low caloric content when hydrated, and its price-performance
effectiveness. Starch may desirably be included in amounts of from about
1% to about 75%, and preferably for various uses, from about 25 to about
60 weight percent based on the total weight of the fiber (dry basis), as
previously described.
The protein fiber generating solution may be provided in any suitable
manner, as by preparing and subsequently combining separate protein
components and xanthan gum polymer solutions, and by initially preparing a
solution comprising both components. In methods in which fibers are formed
which are subsequently comminuted by shear to form an anisotropic
xanthan/protein complex microfragment dispersion, the fiber generating
solution may contain a solubilized protein component and xanthan component
in a particular range to produce anisotropic fibers, and in this regard,
the total solubilized protein and xanthan components should best be in the
range of from about 0.1 weight percent to about 20 weight percent and
preferably in the range of from about 2 weight percent to about 10 weight
percent, based on the total weight of the aqueous fiber generating
solution. The aqueous fiber forming solution may further include other
components, including other dissolved or suspended protein components,
flavoring agents, preservatives and hydrocolloids provided they do not
interfere with the desired anisotropic complex formation. However, as will
be discussed hereinafter in respect to various other aspects of the
present disclosure, xanthan/protein gel complex compositions may also be
formed which may find utility in various food products and manufacturing
methods.
Further in accordance with xanthan/protein dispersion manufacture methods,
the pH of the fiber generating solution is adjusted to a pH at which the
components form a complex, which is preferably within about 2 pH units,
and more preferably within about 1 pH unit, of an optimum isoelectric pH
for the desired complex, to form a fibrous complex under conditions of
mixing which may be utilized in the preparation of xanthan/protein
microfragment dispersions. The fiber formation may occur over a range of
pH approaching the isoelectric point of the xanthan gum - protein complex.
In this regard, for example, for a soy protein isolate-xanthan gum fiber
complex formation, fiber formation may begin near neutral pH and increases
as the pH is adjusted to or near to the isoelectric point of the hybrid
soy protein-xanthan gum complex, which typically may be in the range of
from about 2 to about 5. The fiber formation is spontaneous and does not
require the use of spinning equipment. Once the fibers are formed, they
are made relatively stable to a range of salt and pH conditions by heat
treatment as will be more fully discussed hereinafter. Moreover, the
fibrous network synereses (exudes water), which is desirable in the
minimization of energy intensive drying steps, if drying is desired. The
separation of the fibrous hybrid protein complexes from the liquid phase,
which may contain low molecular weight solutes, effectively removes salts
from the protein-complex while at the same time concentrating the protein
component.
The adjustment of pH to form fibers from the xanthan/protein solution
mixture may be carried out in a variety of ways. In this regard, the
protein fiber generating solution may be provided at a pH significantly
above the isoelectric point of the protein complex fibers, and
subsequently reduced in pH toward the isoelectric point. This pH reduction
may be carried out for example by removal of a cationic counterion (e.g.,
Na+) of the solubilized xanthan gum and/or protein component as by
electrophoresis, or by addition of an edible or food grade acid such as
hydrochloric acid, phosphoric acid, lactic acid, acetic acid, citric acid,
ascorbic acid, carbonic acid or mixtures thereof. The acid appears to
protonate both the carboxylate and the amino groups of the protein to make
the protein less negatively charged so as to link the polymeric chains of
the very negatively charged xanthan gum, to form a gum protein complex
that has a fibrous network. Adjustment of pH may also be carried out by
other appropriate techniques such as by combining an aqueous solution of
the protein component at a predetermined pH at which the protein component
is solubilized with an aqueous solution of the xanthan gum component at a
predetermined pH at which it is solubilized, such that upon combination
the resulting solution has a predetermined pH at or near the isoelectric
point of the desired protein/xanthan gum fibrous complex. In this regard,
it will be appreciated that the protein component may be provided in
aqueous solution in broad ranges of pH at higher and lower pH than its
protein isoelectric point(s), and the xanthan gum, which has substantially
only anionic carboxylic groups, may also be provided in aqueous solution
over a broad range of pH. It will also be appreciated that the pH may be
adjusted by selective anion removal from a combined solubilized protein
and xanthan component solution having low pH, as discussed in U.S. Pat.
Nos. 4,559,233 and 4,563,360, in order to raise the pH to a value
approximating the isoelectric point of a desired protein component-xanthan
gum fibrous complex, or an edible food grade base, such as sodium
hydroxide may be added to such solubilized acidic mixtures.
The fibrous complex forming reaction is best completed or maximized under
complex-forming conditions when the gum-protein mixture is adjusted to a
pH at which the electrophoretic mobility of a desired gum-protein mixture
is substantially zero. Electrophoretic mobility may be measured using
conventional analytical instruments such as a System 3000 electrokinetic
analyzer manufactured by PenKem, Inc., Bedford Hills, N.Y.
Optimal points for hybrid complex formation may be determined by measuring
the isoelectric points of desired complexes, which may be carried out by
measuring the isoelectric point values separately for the reactants, and
adjusting the mixture pH to a value intermediate to the individual pI to
form a sample of the desired complex. The pI of the complex thus formed
may be measured to determine a desired pH for the complex formation as the
control point of the reaction to maximize product yields and achieve the
desired fibrous food texture. The isoelectric point of a protein-xanthan
complex may be selected depending upon the respective proportions of the
components of the complex, and upon the isoelectric points of the
components.
Anisotropic xanthan/protein complex fibers, upon formation, and without
further (e.g., denaturation) treatment, are stable in acidic and neutral
media, but may be dissolved in an alkaline solution (i.e., pH 9.0 or
higher). The complexes tend to redissolve when the pH is greater than
about one pH unit above the pI of the protein component. The stability of
the complex and of microfragmented dispersions produced therefrom may be
enhanced by heat treatment, as will be more fully discussed hereinafter.
The texture of the xanthan/protein complex may be controlled by varying the
ratio of the gum versus the protein. As indicated, the xanthan gum to
protein weight ratio of the complex is desirably within the range of from
about 2:1 to about 1:15, and for reasons of economy, may be in the range
of from about 1:4 to about 1:0 Percentages given herein are weight
percentages, and ratios are weight to weight ratios, unless otherwise
indicated.
Xanthan gums and proteins may also be utilized to form gels when the
xanthan/protein weight ratio in the complex forming solution is relatively
large upon acidification (i.e., a relatively high level of the ionic
polysaccharide) such as from about 1:3 to about 2:1 xanthan:protein ratios
in the complex forming solution and preferably about 1:2 for xanthan/egg
white-whey protein complexes. Other polysaccharides and proteins, as
previously described, may also form gels when the polysaccharide/protein
ratios are similarly relatively high. Microfragmentation of these
polysaccharide/protein gels yields a smooth, creamy and fat-like
foodstuff, which can be used as a fat replacer in a variety of food
products. For example, it has been found that the microfragmented
xanthan/egg white/caseinate (1:1:1) complex-based mayonnaise was bland,
smooth and creamy and the microfragmented xanthan/egg white/caseinate
(1:1:1) complex based frozen dessert was also bland, smooth and creamy,
indicating that these microfragmented polysaccharide/protein gels may be
used as desirable fat replacers in various food products. It is an
advantage of using this type of polysaccharide protein complex that the
protein utilization yield from the complex forming solution is high and
that heating may not be required for stabilization for use in a variety of
food products.
Having generally described manufacture of microfragment dispersions,
various aspects of the invention will be further described with respect to
methods and apparatus schematically illustrated in FIG. 1. As shown in
FIG. 1, an aqueous fiber-forming solution 102 may be prepared by
dissolving suitable protein sources such as whey protein concentrate (WPC,
which is approximately 1/3 whey protein) and egg albumen mixtures and
xanthan gum in a suitable blending mechanism 102 to provide a fiber
generating solution 104 having about 2 weight percent total solids at a
xanthan/whey protein concentrate/egg white weight ratio of 1:4:4, and a pH
of about 6.5.
The temperature at which the protein-gum interaction is carried out may be
utilized to affect the properties of the complex. Softer and finer fibers
may be obtained, if desired, when the gum and the protein are heated to or
above 70.degree. C. before the two polymers are mixed and acidified. In
any event, fiber formation should best be carried out at a temperature of
from about 4.degree. C. to less than about 100.degree. C. or the
temperature at which the particular protein component(s) is denatured
under the processing time conditions used.
The blended component may be progressively transferred along tanks 106,
108, and pumped by means of a suitable pump 110 through a holding complex
formation tube 112, into which is also metered a suitable edible acid 114
by means of metering pump 116, to initiate anisotropic, xanthan/protein
fiber formation. The formed fibers are conducted into a relatively low
shearing screw type pump 118 and from there to a wash/screen belt 120
where the fibers 122 are separated from the remaining whey solution 124
and water washed.
The whey 124 separated from the fiber composition 122 may contain inorganic
salts resulting from the pH adjustment step, and may contain some
unreacted protein, xanthan gum, lactose or other components.
The fibers are heated in cooker 126 to stabilize the fibers, water rinsed
at ambient temperature in wash tank 128, and subjected to
microfragmentation in aqueous slurry by means of high shear device 130.
The washing of fibers prepared from a flavored source of protein such as
whey protein concentrate is an important step in preparing bland
microfragment dispersions, because undesired flavor components may be
substantially removed by such washing. However, it is noted that such
washing is unnecessary if only bland proteins (such as high-quality skim
milk, sodium caseinate, egg white protein or mixtures thereof) are
utilized in the complex formation, or if the flavor components are not
objectionable in the food product which will incorporate the microfragment
dispersion. The microfragmented dispersion having a solids concentration
of 3-7 percent by weight is subsequently subjected to acidification from
edible acid source 136 and centrifugation by centrifuge 132 to provide a
microfragment-depleted supernatant 135 and concentrated, heat stable
microfragmented dispersion 134 having a semisolid, creamy texture and
bland taste, with a solids content in the range of from about 10 to about
25 weight percent. The acid component 136 may include alkaline earth salts
to enhance centrifugation effects. Alternatively, the microfragmented
aqueous dispersion 138 produced by the high shear device 130 containing
from about 3 to about 7 weight percent solids, may be concentrated by thin
film evaporation processes. In this regard, the dispersion 131 may be
introduced into a thin film evaporator 140 such as a Model IST8-48
Turbafilm Processor evaporator of the Votator division of Weldon, Inc. of
Clark, N.J. The Turbafilm processor 140 is a mechanically agitated thin
film evaporator. The dispersion 131 is introduced into the top of the thin
film evaporator 140, which has heated outer cylindrical walls 144 and an
inner rotor. The microfragmented aqueous dispersion forms a thin film on
the heated inner cylindrical wall and the rotor provides mechanical
agitation of the falling product film on the thermal walls to achieve high
heat and mass transfer rates with very viscous materials. The aqueous
dispersion 131 to be processed enters through the inlet above the thermal
section and is distributed in a thin uniform film by the centrifugal
action of the rotor blades. A drying gas (which may be heated if desired)
is continuously introduced into inlet 146, and moist gas containing water
evaporated from the thin aqueous dispersion film is discharged at outlet
148. It is preferred that the system be internally under subatmospheric
pressure, by connecting the discharge 148 to a partial vacuum system.
Turbulence is imparted to the film as it spirals downward, inducing a high
rate of heat transfer into the dispersion film coincident with vapor
formation. The inner wall temperature is desirably maintained at a
predetermined temperature in the range of from about 50.degree. C. to
about 90.degree. C. and the dispersion processing rate and the drying gas
flow coordinated to provide a concentrated aqueous dispersion having from
about 10 to about 30 weight percent and preferably in the range of 15-25
weight percent total solids. The concentrated viscous dispersion 142 exits
through the bottom discharge section while the evaporated water rises
through the separator section and out the vapor outlet 148. The evaporator
may be operated at ambient, or subatmospheric pressures.
The action of the rotor blades keeps the thin film of the aqueous
microfragmented dispersion in continuous turbulent motion, preventing
localized overheating. The Turbafilm processor generally operates with a
rotor tip speed of approximately 30 to 50 feet per second.
A Hydrafilm plowing blade system for the Turbafilm evaporator is utilized
in the embodiment 140. This plowing blade system has a notched blade
design which produces a wall-scraping or film plowing action particularly
suited to high viscosity materials. The plowing blade operates at moderate
tip speed such that it swings outward by centrifugal force into contact
with the liquid film. The combination of viscous drag, shear effect and
instant release of blade pressure results in thorough agitation and film
mixing.
Sufficient water is evaporated to provide an aqueous dispersion having a
solids content in the range of from about 10 to about 30 weight percent
solids, which dispersion may be a very high viscosity product. A rotary
positive displacement pump is coupled to the discharge head of the
Turbafilm processor, so that the concentrated product can be moved quickly
and easily under positive pressure.
While centrifugation and thin film evaporation concentration processes have
been described, other concentration methods may also be utilized. In this
regard, the microfragmented aqueous dispersion may be subjected to
ultrafiltration or reverse osmosis treatment utilizing a suitable
permeable membrane, to remove water and low molecular weight dissolved
salts and nonionic components. Diafiltration, in which fresh water is
introduced into the dispersion, followed by ultra-filtration, may be used
to wash the dispersion, if desired.
Although the method of FIG. 1 has been particularly described with respect
to a microfragmented anisotropic dispersion of xanthan/whey protein-egg
protein complex fibers, other water soluble proteins and polysaccharides
as previously described, may also be utilized to prepare microfragmented
dispersions in accordance with the present invention. In this regard, for
example, casein such as provided by fresh skim milk, skim milk powder or
as bland sodium caseinate, other vegetable proteins such as peanut protein
isolate, such as provided by vegetable proteins and mixtures thereof may
be utilized as the solubilized protein component to form gelled or fibrous
hybrid protein complexes in accordance with the present disclosure. These
complexed xanthan/protein fibers are relatively bland and may differ in
color and texture. For example, xanthan/casein fibers are white and tough,
while xanthan/peanut protein isolate and xanthan/soy protein fibers are
somewhat softer than the xanthan/casein fibers.
Upon formation, the complexed xanthan gum-protein fibers may be readily
separated from the remaining aqueous phase component in any suitable
manner, as by filtration or centrifugation. For example, such fibers may
be harvested by separating them from the aqueous phase, washing them with
water, and pressing them in a cheese-press to provide meat-like fibers
that contain generally from about 65 to about 80 weight percent moisture,
and typically about 65 percent by weight moisture.
The fibers of xanthan gum--soy protein complex tend to soften and become
slightly slimy above pH 5.5 perhaps because the gum-protein complex is
very negatively charged and has more charge characteristics of xanthan gum
at or above pH 5.5. An important feature of preferred microfragmented
dispersions in accordance with the present invention is that substantial
stability and other improved properties may be provided in the
microfragmented xanthan/protein dispersion if the preformed fibers are
subjected to a heat treatment, such as by boiling in water, for a time
sufficient to denature at least about 50 percent of the protein
components. It appears that such treatment denatures the protein or the
complex as a whole so as to prevent the dissociation and/or dissolution of
the gum-protein complex.
Heat treatment of the protein-gum complex not only results in stabilization
of the complex to retain its firmness, but may also be utilized to
pasteurize the complex. In addition, by varying the temperature and the
time of heating, different degrees of firmness and stability of the
complex can be obtained, as desired.
The protein complexing agent may also comprise suitable hydrocolloids in
addition to xanthan gum. In this regard, for example, carob gum is very
inexpensive compared to xanthan gum and is demonstrated to have strong
interaction with xanthan gum. Fibrous ternary complexes of soy protein
isolate, xanthan gum and carob gum may be prepared by mixing the two gums
to form an aqueous suspension, and subsequently adding the desired
protein.
The moisture content of the anisotropic, hydrated fibers will generally be
in the range of 60 to about 90 percent by weight. However, the fibers, as
precipitated, or after heat stabilization may be substantially reduced in
moisture content to provide a low moisture fiber product which retains its
fiber integrity. Fiber compositions having reduced moisture content may be
provided which have longer shelf life and easier handling for shipping and
storage. The dried complex may be readily rehydrated by contact with
water.
The microfragmented xanthan/protein complex dispersion may be utilized in a
wide variety of food products. The dispersions find particular utility in
frozen desserts, dressings, spreads, baked goods, processed cheese and
cheese analog products, cultured dairy products, comminuted meat products
and analog comminuted meat products such as low fat hot dogs and luncheon
meats, as well as sauces, soups and gravies.
While microfragmented ionic polysaccharide/protein complex dispersions such
as xanthan/protein complex dispersions of high quality may be prepared by
methods such as illustrated in FIG. 1, other production methods may also
be desirable. In this regard, illustrated in FIG. 13 is a schematic
diagram illustrating a specific embodiment of a continuous method for
manufacture of xanthan/protein complex microdispersions in which the
solubilized xanthan and protein components are continuously conducted
through a zone of high specific turbulent dissipation rate under complex
forming conditions.
As shown in FIG. 14, in accordance with continuous processing methods, a
continuous stream 1402 of a xanthan/protein solution having a xanthan to
protein weight ratio in the range of from about 1:1 to about 1:20 is
provided by metering pump 1404 from holding tank 1406 and into a shearing
zone 1408 of high turbulent energy dissipation rate. The shearing zone may
be a high pressure, fluidic, acoustic or mechanically driven mill zone,
such as a colloid or pin mill high shear zone. Within the zone, the ionic
polysaccharide/protein solution such as a xanthan/protein solution is
acidified in order to initiate the formation of a complex precipitate
under high shear conditions. The fragmented or microfragmented dispersion
conducted from the high shear mixing zone may be heated to a denaturation
temperature for the complex by heat exchanger 1410 and pumped under high
pressure through one or more high pressure cell disrupter homogenizers
1412. As indicated, a plurality of high pressure homogenizers may be
connected in series with charge dispersion recycle 1414 to achieve a
desired degree of microfragmentation. An advantage of the method
illustrated in FIG. 14 is that it may utilize relatively high solids
content of the complex such as a xanthan/protein complex, so that the
finished dispersion may be used directly without a concentration step.
Similarly illustrated in FIG. 15 is a schematic diagram illustrating a
specific embodiment of a batch-type method for manufacture of ionic
polysaccharide/protein dispersions such as xanthan/protein complex
microfragment dispersions in which the solubilized xanthan (or other ionic
polysaccharide) and protein components are conducted through a zone of
high specific turbulent dissipation rate as complex forming conditions are
developed in the batch undergoing processing.
As shown in FIG. 15, a xanthan/protein solution prepared in a holding tank
1502 may be pumped initially into a homogenizer circuit including a pump
1504, a high pressure fluidic homogenizer 1506, a heat exchanger and
storage tank 1508. After charging the circuit with the xanthan/protein
solution, the solution is conducted through the homogenizer shear device
1506 while the pH is gradually lowered by metering of an acid stream from
acid tank into the fluidic circuit. The heat exchanger 1508 is utilized to
maintain a desired processing temperature. The batch processing
illustrated in FIG. 14 may also be utilized with relatively high
concentrations of xanthan gum and protein. Upon completion of the
microfragmentation, the finished xanthan/protein complex dispersion may be
discharged from outlet 1512 to begin the production process for
incorporation into a variety of food products.
Xanthan gum is relatively expensive, and may have limited efficiency in
complexing certain protein components, thereby involving relatively higher
amounts of xanthan gum in complex formation and potentially leaving
uncomplexed protein components in the fiber whey solution. The present
invention is also directed to methods for manufacturing edible, stable
polysaccharide/protein complex carboxymethyl cellulose fiber compositions
which have a fibrous body and texture, through the use of high molecular
weight, highly substituted food grade carboxymethyl cellulose as a protein
complexing component. Such materials may be used to prepare
microfragmented ionic polysaccharide/protein complex aqueous dispersions
in accordance with the present invention.
In accordance with various aspects of the present disclosure, methods for
edible carboxymethyl cellulose/protein fiber manufacture are provided
comprising the steps of providing an aqueous protein fiber generating
solution, as previously described.
The fiber generating solution for carboxymethyl cellulose/protein fiber
generation further includes a solubilized high molecular weight, highly
substituted food grade carboxymethyl cellulose polymer component. By high
molecular weight, highly substituted food grade carboxymethyl cellulose is
meant cellulose, which is a poly (glucose) saccharide, having an average
degree of substitution of carboxymethyl groups on the hydroxyl groups of
the anhydro-D-glucopyranose units of the cellulose in the range of from
about 0.8 to about 1.0 per anhydro-D-glucopyranose unit, and preferably
about 0.9 and having a weight average molecular weight of at least about
100,000 daltons. Commercial food grade sodium carboxymethyl cellulose may
have an average degree of carboxymethyl substitution between 0.4 and 0.9;
however, it has been determined that carboxymethyl cellulose having an
average degree of carboxymethyl substitution of 0.7 or less does not
readily form fibers under the conditions of the present methods. While a
degree of substitution of up to 3.0 may be provided, materials having a
degree of substitution over 0.9 are not approved for food use by the U.S.
Food and Drug Administration. The properties of sodium carboxymethyl
cellulose can be controlled by varying the uniformity of substitution, the
degree of substitution and the molecular weight. A discussion of the
physical and chemical properties of various carboxymethyl cellulose
components may be found in Industrial Gums, R. L. Whistler, Ed., Academic
pres, N.Y. (1973), p. 643.
As indicated, carboxymethyl celluloses having a relatively low degree of
carboxymethyl group substitution do not provide fibrous protein complexes
in accordance with the present invention. However, by utilizing
carboxymethyl cellulose having a degree of substitution in the range of
from about 0.8 to about 1.0, and more preferably about 0.9 stable fibrous
complexes may be prepared in accordance with the method aspects of the
present invention, which may be utilized to contribute a fibrous or meat
analog characteristic to food products, or which may be microfragmented
after stable fiber formation to provide smooth, creamy aqueous
microfragment dispersions, as previously described.
A relatively high molecular weight is also believed to be an important
factor in complex fiber formation. In this regard, carboxymethyl cellulose
(albeit not a food grade material), having a degree of substitution of
about 1.2, but a relatively low molecular weight of 70,000 daltons has
failed to form fibers under these conditions which produce fibers using
the appropriate carboxymethyl cellulose as previously described.
The protein fiber generating solution may be provided in any suitable
manner, as by preparing and subsequently combining separate protein
component and highly substituted food grade carboxymethyl cellulose
solutions, and by initially preparing a solution comprising both
components. Further in accordance with the present disclosure, the fiber
generating solution should contain a solubilized protein component and
highly substituted carboxymethyl cellulose component in a particular
range, and in this regard, the total solubilized protein and highly
substituted carboxymethyl cellulose components should be in the range of
from about 0.1 weight percent to about 10 weight percent, and preferably
from about 4 to about 6 weight percent based on the total weight of the
aqueous fiber generating solution. Carboxymethyl cellulose is typically
less viscous than xanthan gum, and may be used in higher concentration
under various conditions while still providing fibrous complexes.
The aqueous fiber forming solution may further include other components,
including other dissolved or suspended protein components, flavoring
agents, preservatives and hydrocolloids, as previously described.
The complex forming solution may also include water solubilized,
substantially nonionic edible polysaccharides such as dissolved starch,
solubilized agar and agaroids, dissolved guar gum, dissolved carob gum,
water soluble dextrans, etc. in the amounts, and using the procedures as
previously described. Such nonionic polysaccharide components may become
entangled and enmeshed with the ionic polysaccharide/protein complex which
is formed upon pH adjustment of the complex forming solution. It is
desirable that the complex contain at least about 15 weight percent of
solids, and preferably for a variety of uses, at least about 20 weight
percent solids, and the amount and type of nonionic polysaccharide may be
adjusted to provide a desired solids level.
Further in accordance with the method, the pH of the fiber generating
solution is adjusted to a pH at which the components form a complex, which
is preferably within about 2 pH units of an optimum isoelectric pH for the
desired complex, to form a fibrous protein-polysaccharide complex under
conditions of mixing of the fiber forming solution, as previously
described. In this manner, hybrid protein complexes may be formed which
have a fibrous, meat-like texture. The fiber formation may occur over a
range of pH approaching the isoelectric point of the particular highly
substituted carboxymethyl cellulose/protein complex. In this regard, for
example, for a high molecular weight, highly substituted carboxymethyl
cellulose/egg protein sodium caseinate complex, fiber formation may begin
near neutral pH and increases as the pH is adjusted to or near to the
isoelectric point of the complex, which typically may be in the range of
from about 1 to about 5.
The texture of the carboxymethyl cellulose/protein complex fibers may be
controlled by varying the ratio of the fiber forming polysaccharide
component versus the protein component. The desired fiber forming
polysaccharide to protein weight ratio is within the range between 1:2 and
1:15, and more preferably in the range of from about 1:4 to about 1:10.
The adjustment of pH to form fibers from the highly substituted
carboxymethyl cellulose/protein mixture may be carried out in a variety of
ways, as previously described. The fibrous complex reaction is completed
or maximized when the highly substituted carboxymethyl cellulose/protein
mixture is adjusted to a pH at which the electrophoretic mobility of a
desired highly substituted carboxymethyl cellulose/protein mixture is
substantially zero.
The shape and size of the highly substituted carboxymethyl
cellulose/protein complex fibers may be controlled by the degree of shear
or mixing applied to the fiber forming solution during pH adjustment.
After formation of the highly substituted carboxymethyl cellulose/protein
complex fibers, it is important to heat the fibers to stabilize them in
fiber form so that they are capable of withstanding a broad range of pH,
mechanical shear and ionic conditions, as well as stability in interaction
with a broad range of other food components. Such stabilization may be
carried out by heating the fibers to a temperature of at least about
70.degree. C. for at least 30 seconds or equivalent time temperature
relationships, and more preferably at least about 95.degree. C. for at
least about 5 minutes to denature the protein within the complex at least
about 40 percent, and more preferably at least 90% to stabilize the
complex. Such denaturation may be readily measured by differential
scanning calorimetry ("DSC"). Desirably the fibers will be heated to a
temperature of about 100.degree. C. as by boiling in water or steam
injection, for at least about 5 minutes, (e.g., 3-5 minutes) to
substantially fully denature the protein component of the complex. The
heat dependence of denaturation will typically vary with pH, with the
complex being easier to denature at lower pH values. By "denatured" is
meant loss of native secondary and tertiary structure, such as measured by
DSC. Denaturation may result in substantial disulfide crosslinking, as
measured by gel electrophoresis, which will also help stabilize the
complex.
In addition to the high molecular weight carboxymethyl cellulose/protein
fibrous complexes previously described, it has also been discovered that
fibrous complexes may be prepared from lambda carrageenan and solubilized
protein solutions. Such fibers may be used in food products directly as
fibers, or may be subjected to high shear microfragmentation processing
such as previously described.
In accordance with these aspects of the present disclosure, methods for
edible lambda carrageenan/protein fiber manufacture are provided
comprising the steps of providing an aqueous protein fiber generating
solution comprising a solubilized edible protein polymer component and a
lambda carrageenan component.
Such a protein fiber generation solution may, for example, comprise a
solubilized edible protein polymer component as previously described.
As indicated, the fiber generating solution for carrageenan/protein fiber
generation includes a solubilized food grade lambda carrageenan.
Carrageenans are structural polysaccharides of red sea plants such as
Chondus crispus and Gigartina stellata. There are several varieties of
carrageenans which may be extracted from red sea plants for food use,
including kappa, lambda and iota carrageenans. Carrageenans are strongly
charged anionic polyelectrolytes of high molecular weight and regular
configuration which have anionic sulfate ester groups regularly disposed
along a polysaccharide backbone. Lambda carrageenan has a general linear
structure having substantially three pendant sulfate groups for each two
monosaccharide groups along the polymer backbone:
##STR1##
Kappa carrageenan and iota carrageenan have significantly less ester
sulfate than lambda carrageenan, with iota carrageenan having
approximately one sulfate group per monosaccharide group, and kappa
carrageenan having approximately one sulfate group for each two
monosaccharide groups along the backbone. Kappa carrageenan and iota
carrageenan alone do not form fiber complexes from protein solutions in
accordance with the present invention. A discussion of the physical and
chemical properties of lambda carrageenan may be found in Industrial Gums,
R. L. Whistler, Ed., Academic Press, N.Y. (1973).
The lambda carrageenan component when fiber complex generation is desired,
will desirably contain at least about 50 weight percent lambda carrageenan
based on the total weight of iota, kappa and lambda carrageenan, and more
preferably at least about 60 weight percent lambda carrageenan, based on
the total weight of the carrageenan. The Lactarin PS189 product of FMC
Corporation, which contains about 50 percent lambda carrageenan, 20-30
percent kappa carrageenan and 20-30 percent dextrose by weight, has been
successfully utilized to provide fibrous complexes as described herein.
The Viscarin GP109 product (50-60% lambda and 40-50% Kappa) and the
RE9345/6 products of FMC Corporation (100% lambda) are also examples of
lambda carrageenan products.
In aqueous solution, the highly charged mutually repelling sulfate ester
side chains, which are disposed along the polysaccharide backbone of
lambda carrageenan, are believed to provide a relatively linear structure,
which is further believed to be an important factor in the provision of
fiber complexes in accordance with the present invention. A relatively
high molecular weight is also believed to be an important factor in
complex fiber formation.
The lambda carrageenan component may be used with highly substituted,
highly molecular weight carboxymethyl cellulose components, xanthan gum or
mixtures thereof, or with other anionic polysaccharide gums in amounts
which do not prevent fiber formation. When used with other potential
complex fiber-forming polysaccharides such as xanthan gum, and/or
carboxymethyl cellulose, the relative proportions of these components may
vary over a wide range. The carboxymethyl cellulose or other anionic
polysaccharides may be of "border line" fiber forming capability, with the
lambda carrageenan, xanthan gum and/or the highly substituted, high
molecular weight carboxymethyl cellulose component contributing a strong
fiber forming capacity. When used with other non-fiber forming
polysaccharides such as iota and kappa carrageenan, carboxymethyl
cellulose, pectins and alginates, which alone do not self-assemble under
appropriate conditions with proteins to form fibers, the proportions of
fiber-forming polysaccharide such as lambda carrageenan to the non
fiber-forming polysaccharide should be sufficient to provide spontaneous
fiber formation.
When the lambda carrageenan is dissolved with non fiber-forming anionic
polysaccharides in the fiber-forming solution, the lambda carrageenan
should desirably comprise at least about 50 weight percent of the anionic
polysaccharide components, and more preferably at least about 75 percent.
The protein fiber generating solution may be provided in any suitable
manner, as by preparing and subsequently combining separate protein
component and lambda carrageenan, and by initially preparing a solution
comprising both components. Further in accordance with the present
disclosure, the fiber generating solution should contain a solubilized
protein component and lambda carrageenan in a particular range, and in
this regard, the total solubilized protein and lambda carrageenan
components should be in the range of from about 0.1 weight percent to
about 10 weight percent, preferably from about 2 to about 8 weight
percent, and more preferably from about 4 to about 6 weight percent based
on the total weight of the aqueous fiber generating solution.
The aqueous fiber forming solution may further include other components,
including other dissolved or suspended protein components, flavoring
agents, preservatives and hydrocolloids.
As previously described, the complex forming solution may also include
water solubilized, substantially nonionic edible polysaccharides such as
dissolved starch, solubilized agar and agaroids, dissolved guar gum,
dissolved carob gum, water soluble dextrans, water or alkali soluble
edible grain bran and/or hemicellulose constituents such as solubilized
wheat gum, solubilized wheat bran, solubilized oat bran and solubilized
corn bran constituents, as well as mixtures of such nonionic
polysaccharides.
As previously described, starch may desirably be included in the complex
forming solutions, and in the precipitated complexes, in amounts of from
about 1% to about 75% by weight, based on the total weight of the
polysaccharide/protein complex on a dry basis. For various uses, the
starch will preferably be included in the precipitated complexes in an
amount in the range of from about 25 percent to about 60 percent by
weight, based on the total weight of the complex on a dry basis.
Further in accordance with the method, the pH of the fiber generating
solution is adjusted to a pH at which the components form a complex, which
is preferably within about 2 pH units of an optimum isoelectric pH for the
desired complex, to form a fibrous protein-polysaccharide complex under
conditions of mixing of the fiber forming solution. In this manner, hybrid
protein complexes may be formed which have a fibrous-meat like texture, as
previously described. The fiber formation may occur over a range of pH
approaching the isoelectric point of the lambda carrageenan/protein
complex. In this regard, for example, for a high molecular weight lambda
carrageenan/egg white protein/sodium caseinate complex, fiber formation
may begin at moderately high acidic pH values and increases as the pH is
adjusted to or near to the isoelectric point of the complex, which
typically may be in the range of from about 1 to about 5. The fiber
formation is spontaneous and does not require the use of spinning
equipment. Moreover, like various other fibers described herein, the
fibrous network synereses (exudes water), which is desirable in the
minimization of energy intensive drying steps.
The texture of the lambda carrageenan/protein complex fibers may be
controlled by varying the ratio of the fiber forming polysaccharide
component versus the protein component. The desired fiber forming
polysaccharide to protein weight ratio is within the range between 1:2 and
1:15, and more preferably in the range of from about 1:4 to about 1:10.
The adjustment of pH to form fibers from the lambda carrageenan/protein
mixture may be carried out in a variety of ways, as previously described.
The fibrous complex reaction is completed or maximized when the lambda
carrageenan/protein mixture is adjusted to a pH at which the
electrophoretic mobility of a desired lambda carrageenan/protein mixture
is substantially zero.
After formation of the lambda carrageenan protein complex fibers, it is
important to heat the fibers to stabilize them in fiber form so that they
are capable of withstanding a broad range of pH, mechanical shear and
ionic conditions, as well as stability in interaction with a broad range
of other food components. Such stabilization may be carried out by heating
the fibers to a temperature of at least about 70.degree. C. for at least
30 seconds, and more preferably at least about 95.degree. C. for at least
about 5 minutes to denature the protein within the complex at least about
40 percent and more preferably at least about 90 percent, and stabilize
the complex. Desirably the fibers will be heated to a temperature of about
100.degree. C. as by boiling in water or steam injection, for at least
about 5 seconds to substantially fully denature the protein component of
the complex. The heat dependency of denaturation will typically vary with
pH, with the complex being easier to denature at lower pH values. By
"denatured" is meant that the protein has lost its native secondary and
tertiary structure, such as measured by differential scanning calorimetry
("DSC"). Denaturation may result in substantial disulfide crosslinking,
such as measured by gel electrophoresis, which will also help stabilize
the complex.
A specific example of preparation of lambda carrageenan (or high molecular
weight carboxymethyl cellulose)/protein fibers for subsequent high shear
microfragmentation is shown in FIG. 17. An aqueous protein solution such
as a mixture of undenatured egg white and undenatured sodium caseinate
1700 is provided at a protein concentration of 8.0 weight percent.
Similarly, a lambda carrageenan solution 1702 is prepared by dissolving
lambda carrageenan in water, at a level of about 1.0 weight percent. The
solutions 1700, 1702 may be combined in desired ratio to provide a fiber
generating solution 1714 having about 4 weight percent protein and 0.5
weight percent lambda carrageenan at a pH of about 6.5. Alternatively, the
components may be combined directly with water to form the solution 1714.
The pH adjustment may be carried out by addition of hydrochloric acid to
provide fibers 1716 and a whey phase 1718 which may be separated by
appropriate means.
The weight percent total solids of the fiber generating lambda
carrageenan/protein solution 1714 in water may typically be varied within
the range of from about 0.1 weight percent to about 8 and preferably from
about 0.25 to about 4. The water content of the fiber generating solution
(as well as the ionic strength) is important for the complexed polymers to
form a fibrous network. Fiber formation should desirably be carried out at
a temperature which is less than the denaturation temperature of the
protein component(s), and preferably from about 10.degree. C. to about
50.degree. C.
The whey 1718 separated from the fiber composition 1716 may contain
inorganic salts resulting from the pH adjustment step, and may contain a
small amount of lambda carrageenan or other components, particularly of a
blend of lambda carrageenan and another less efficient anionic
polysaccharide is used as the anionic complexing agent. However, the
lambda carrageenan is a highly efficient complexing agent, which minimized
uncomplexed protein and/or lambda carrageenan in the whey component. The
inorganic salts may be removed, at least in part by appropriate means such
as through the use of selectively permeable membranes, electrodialysis
and/or ion exchange resins, to provide a deionized whey 1722, which may be
utilized in the provision of the protein and lambda carrageenan solutions
1700, 1702.
Various proteins utilized in aqueous protein/gum complexes in accordance
with the present disclosure may contribute some degree of off-flavor or
undesirable flavor components to complexes even though the complexes are
substantially blander than the protein, while other proteins such as high
quality skim milk protein and bland, high quality sodium caseinate may
have a very low flavor profile. For example, whey protein sources such as
whey protein concentrate may contribute fermentation or other flavor
components which may impart undesirable flavors to polysaccharide complex
dispersions formed utilizing such whey protein concentrate materials. As
described hereinabove, fibers or nonfibrous complex precipitates formed
from such whey protein or other flavored protein and a polysaccharide may
be washed in water to remove such undesirable flavor components before
microfragmentation processing, to provide an extremely bland
microfragmented or microparticulate aqueous dispersion. However, it may be
desirable to form dispersions directly without an intermediate washing
step for such materials. Accordingly, it is also contemplated herein that
the protein components may be pre-cleaned by precipitation and
redissolution procedures, followed by re-precipitation in the preparation
of an aqueous complex dispersion. In this regard, such a clean-up method
may be carried out by forming a solution of a solubilized protein as
previously described such as whey protein, casein, egg white protein,
vegetable protein or mixtures thereof, with an ionic polysaccharide as
previously described, such as xanthan, pectin, carrageenan, gellan,
carboxymethyl cellulose, chitosan and mixtures thereof at a weight ratio
of protein/gum in the range of from about 2:1 to about 15:1 and preferably
in the range of from about 6:1 to about 10:1, and a solids content of less
than 20 weight percent (e.g., 5 weight percent) of the solution at a
suitable pH for dissolution (e.g., pH 6-8), to form a precleaning
solution. Absorbing material such as activated carbon and absorbing clays
may be mixed into the precleaning solution to adsorb undesirable flavor or
color components if desired. The precleaning solution may be filtered or
centrifuged to separate any undissolved components, including such
adsorbing materials with associated components.
Also in accordance with the method, the pH of the precleaning solution is
subsequently adjusted to precipitate a protein/polysaccharide complex
without denaturing the protein. In this regard, the pH may be adjusted to
a pH in a precipitation range about the isoelectric point of the
polysaccharide/protein complex in an appropriate manner, such as by
addition of edible acid for an anionic polysaccharide-protein precleaning
solution, by addition of edible base to a cationic polysaccharide/protein
precleaning solution, or electrodialysis procedures to similarly adjust
the pH.
For anionic polysaccharide/protein precleaning solutions, the initial
precipitation may be carried out by addition of acid including addition of
edible acid such as HCl, acetic acid, carbon dioxide, lactic acid and
mixtures thereof, where appropriate and where such addition causes
precipitation, and/or by electro-deionization techniques such as
electrodialysis which are applied to remove cations from the solution to
lower the pH. Precleaning solutions of ionic polysaccharide and protein
may also be prepared under acidic conditions where appropriate, with
raising of the pH to or near the isoelectric point being utilized for
precipitation.
The precipitated protein/polysaccharide complex is separated from the
syneresed aqueous component of the solution (and optionally washing the
precipitate) without denaturing the protein. Such separation may be
carried out by centrifugation, filtration, and/or pressing of the
precipitate. Optionally, the precipitate may be washed with clean water.
In this step, flavor components which are not combined with the
precipitated complex are removed with the syneresed liquid, and any wash
water.
The precipitated ionic polysaccharide/protein complex is subsequently
redissolved in aqueous solution by adjusting the pH to a pH at which the
precipitated complex redissolves (e.g., pH 6-8 for an anionic gum-protein
complex), to form an aqueous, flavor purified, polysaccharide/protein
complex forming solution. Redissolution should be carried out prior to any
heating of the complex which would denature the material and prevent
redissolution of the complex. The pH of the aqueous, flavor purified,
ionic polysaccharide/protein complex forming solution is subsequently
adjusted such as by reducing the pH to a protein/gum complex precipitation
range, to form, directly or indirectly, an aqueous complex dispersion.
The precipitation/washing/redissolution procedure may be carried out
several times, if desired. The redissolved protein/gum solution may
desirably have a total protein/gum solids content in the range of from
about 2 to about 25 weight percent and may be used to directly form
aqueous protein/gum complex dispersions such as in the continuous
processing apparatus.
By combining a pre-cleaning treatment with an in-situ
acidification/homogenization process at a desired solids content in the
10-20 weight percent range, an inexpensive continuous process for
producing a flavor-free aqueous protein/gum dispersion from a variety of
protein sources may be provided.
For example, a "pre-cleaned" solution having about 5 weight percent
protein/gum solids content may be continuously acidified in a (preferably
two stage) homogenizer, "microfluidizer" or "cell disruptor" stream at a
point immediately preceding the homogenizer orifice to produce an aqueous
dispersion. A fluidic ultrasonic homogenization device such as a Sonolator
(e.g., as described in U.S. Pat. No. 4,765,194), in which the output jet
impinges on a knife edge to generate vortices which promote anisotropic
mixing and anisotropic, elongated protein/polysaccharide particle
formation, may also be utilized. Such direct acidification may be carried
out at relatively high solution solids content (e.g., from about 15 to
about 20 weight percent solids), which produces a high solids content
dispersion without a subsequent concentration step such as centrifugation
or thin film evaporation.
When using xanthan gum as the ionic polysaccharide component of the
precleaning solution, it is noted that the syneresed solution may contain
protein components which are not complexed with the xanthan gum. As shown
in FIG. 18, such protein components may be recovered by addition of
another complexing gum, such as gellan, carrageenan (i.e., kappa and/or
lambda), and/or carboxymethyl cellulose which complexes with the remaining
protein components. These precipitates may also be washed and redissolved
by pH adjustment as previously described, to form complex-generating
solutions, separately or in combination with the xanthan/protein complex
precipitate component. The precleaned ionic polysaccharide/protein
solutions may be used to prepare bland gel and fibrous microfragmented
complexes, as previously described.
While this procedure has been particularly described for the formation of
protein/anionic gum complexes, similar procedures may be utilized for
protein/cationic gum complexes such as egg white/whey protein complexes
with cationic gums such as chitosan.
The various ionic polysaccharide/protein complex fibers and aqueous
dispersions may be provided which have excellent stability in food
products at high temperature. However, it may be desirable to provide
aqueous microfragment dispersions which present a substantial physical and
textural change with temperature. In this regard, the present disclosure
is also directed to aqueous dispersions of thermoreversible ionic
polysaccharide/protein complexes which are in precipitated, complexed gel
form below a solidification temperature, which depends on the composition
of the complex, and which redissolve above the solidification temperature.
Desirably, the solidification temperature may be selected by proper
formulation of the thermoreversible gel and consideration of the
interaction conditions (e.g., pH, ionic species) of the food product in
which the aqueous dispersion is utilized, to occur within a desired
temperature range to impart unique characteristics to the food product.
For example, an aqueous dispersion of a thermoreversible ionic
polysaccharide/protein complex gel utilized as a bulking agent or fat
substitute in a food product such as a frozen dessert in accordance with
the present disclosure, may have a solidification temperature in the range
of 70.degree.-95.degree. F. so that it may give the sensation of melting
in the mouth of the consumer in a manner similar to milkfat.
Similarly, low fat process cheeses, analog cheeses and natural cheeses
which employ the aqueous dispersion as a fat substitute may utilize an
aqueous dispersion of a thermoreversible gel having a solidification
temperature in the range of 100.degree. F.-160.degree. F. to provide
improved melting characteristics, despite reduction or absence of milkfat
in the cheese product.
The thermoreversible gel should not interact below the solidification
temperature to form a gel, so that an aqueous dispersion of the
thermoreversible gel particles remains a discrete dispersion in the food
product in which it is incorporated so long as the temperature is below
the solidification temperature.
It is also desirable that the thermoreversible gel particles of the aqueous
dispersion have a solids content of at least about 5 weight percent, and
preferably in the range of from about 15 to about 50 weight percent
solids. In this regard, it is noted that an aqueous dispersion of
particles of a thermoreversible gel having a solids content of about 45
weight percent may form a dispersion of about two thirds by volume
continuous aqueous phase, and one third by volume of the dispersed,
discrete gel particles, which has an overall total solids content of about
15 weight percent.
Kappa carrageenan and ionic agaroids are desirable thermoreversible gel
forming ionic polysaccharides. Gelatin is a particularly desirable protein
component for complex formation with kappa carrageenan. Thermoreversible
kappa carrageenan/gelatin gels described as "C-Gel 35 Products" are
described in U.S. Pat. No. 4,684,553, which is incorporated by reference
herein. Desirably, C-Gel products may be prepared employing from about 1
to about 4 weight percent of kappa carrageenan, and from about 4 to about
24 weight percent gelatin in water to provide a kappa carrageenan to
gelatin ratio in the range of from about 1:6 to about 1:1 on a dry basis.
Other components such as flavoring agents, other polysaccharides, and
other proteins may be included in the C-Gel product.
The thermoreversible C-Gel may be prepared by dissolving the carrageenan
and gelatin components in the desired amount of water at an elevated
temperature (e.g., 160.degree.-175.degree. F.) and cooling the solution to
form a gel having a solids content of at least about 5 and preferably at
least 10 weight percent. The gel may be ground at a temperature below the
solidification temperature to form gel particles, which may be mixed with
additional water, and subjected to high shear microfragmentation such as
by multiple passes (e.g., at least 4) through a homogenizer or cell
disruptor as previously described at a homogenization pressure
differential of at least about 5,000-20,000 psi, at a temperature below
the solidification temperature of the gel to produce an aqueous
microfragmented dispersion of thermoreversible gel particles having a
largest dimension less than about 15 microns, preferably less than about
10 microns, and more preferably less than about 5 microns. The resulting
aqueous dispersion may be used alone, or with another fat substitute
material, as a fat substitute or bodying agent in a wide variety of food
products such as frozen desserts, and cheeses in which reduced viscosity
or body is desired at an elevated temperature. For example, the dispersion
may be introduced into the skim or low fat milk used in a cheese make at a
level of 2-30 weight percent, based on the total solids content, prior to
fermentation to produce a cheese product, or may be blended with a sour
cream or cream cheese product to provide a reduced calorie product.
Such thermoreversible microfragment dispersions may be blended with other
microfragmented dispersions as described herein to provide food products
having desirable characteristics.
Both intact and microfluidized fibers of xanthan/whey protein-egg protein,
or other polysaccharide/protein complexes may exhibit an astringent
mouthfeel sensation for a segment of tasters. The sensation is apparently
variable among the population, and may be observed in the back of the
throat as a "drying, tingling" effect, and may also be experienced on the
front of the tongue or on other soft tissues of the mouth. The sensation
is less apparent for most tasters in products such as frozen desserts and
appears to intensify in low pH food systems, such as salad dressings,
indicating that the effect may be related to dosage, ionic strength, pH
and/or temperature.
Xanthan gum/whey protein-egg protein complexes are unusual in that they may
be astringent but not bitter. Although there may be a sensation of
dryness, salivary flow is not impeded. The main effect, when it occurs,
seems to be epithelial rather than salivary, upon the surface of the
tongue and oral cavity. It is also theorized that cellular dehydration may
underlie the drying sensation.
In accordance with various aspects of the present invention, astringency
may be reduced in a polysaccharide/protein complex by coating the surface
of the complex with a non-astringent agent. The most effective means of
eliminating astringency is post-homogenization gum coating. In this
regard, a microfragmented dispersion of an ionic polysaccharide/protein
complex, such as a xanthan/protein complex is combined with from about 5
to about 20 weight percent of an ionic or neutral gum, or mixture of gums,
based on the total solids weight of the ionic polysaccharide/protein
complex (dry basis). A number of anionic or neutral gums may be used
including xanthan, carboxymethyl cellulose, carrageenan, alginate, locust
bean gum, guar gum and mixtures thereof. The most effective gums are
xanthan and carrageenan. For example, an aqueous microfragmented ionic
polysaccharide/protein complex, such as a xanthan/protein complex having a
2% to 10% solids content may be mixed in a low shear mixer, such as a
Hobart mixer or a Breddo mixer, with an amount of gum equal to 5% to 20%
of the weight of the xanthan/protein complex. The gums are sifted in dry
to the microfragmented xanthan/protein complex dispersion as it is being
mixed on the low shear device. It is theorized that allowing the gums to
hydrate in contact with the complex allows the gums to interact and coat
the complex, thus reducing exposure of astringency-causing portions of the
microfragmented protein/xanthan complex.
The microfragmented complex may also be coated with an agent such as an
edible fatty emulsifier such as stearoyl lactylate, monoglycerides or
lecithin or a film-forming polysaccharide such as alginate and locust bean
gum. It is theorized that such a coating prevents interaction with the
epithelial tissues of the mouth.
Astringency may be caused by exposed segments of the protein or
carbohydrate which interact with cells on the surface of the mouth or
tongue. Coating of the polysaccharide/protein complex particles with a
thin layer of gum, surfactant such as sodium stearoyl lactylate and/or fat
in accordance with the present invention provides a physical barrier to
this interaction.
The precipitated complex particles may also be coated with polysaccharides
to reduce astringency. Encapsulation or "blocking" (the specific
elimination or shielding of reactive sites in xanthan or proteins with
polysaccharides) may also be utilized to reduce astringency.
In this regard, for example, calcium alginate and locust bean gum have been
used for encapsulation and/or blocking. Sodium alginate was mixed with a
microfragmented dispersion of xanthan/protein complex, and then was either
allowed to gel with the natural calcium present in the complex or was
gelled by the addition of calcium acetate. Astringency may also be reduced
by reduction or masking of sulfhydryl groups on the surface of the
dispersion particles.
As indicated, while the preparation of aqueous microfragmented dispersions
may be carried out by subjecting relatively large fibers or particles of
precipitated polysaccharide/protein complex to intense shear in an aqueous
medium, polysaccharide/protein complex dispersions having a smooth creamy
texture and mouthfeel may also be provided by other processing methods. In
this regard, microparticulate polysaccharide/protein complexes may be
prepared by forming an aqueous complex generating solution of a
solubilized protein component, as previously described, and a complexing
ionic polysaccharide component as previously described, for the protein
component, which may contain from about 1 to about 38 weight percent
solids, based on the total weight of the solution. Also in accordance with
the aspects of the present disclosure, a hydrophobic working liquid is
provided which is immiscible with the aqueous complex generating solution.
The immiscible working fluid may be an edible oil such as a vegetable oil,
or may be an inert non-polar organic solvent alkanes, esters, higher
alcohols, etc., as well as compressed propane, ethane or butane which may
readily be removed from the finished product. Also in accordance with the
method, a water-in-oil emulsion of the aqueous-complex-generating solution
is formed in the hydrophobic working liquid, and the pH of the emulsified
aqueous complex-generating solution emulsified in the working liquid is
adjusted to form precipitated complex particles in the emulsified aqueous
phase. The emulsification step may be carried out in a batch or continuous
mode. The acidification may be carried out by addition of an acidic gas
such as hydrogen chloride or carbon dioxide to the emulsion, preferably
under pressure, or an aqueous or hydrocarbon solubilized acid to the
emulsion. An acid generating component such as an edible lactone which
produces an acid upon hydrolysis may also be utilized. The use of edible
emulsifiers such as lecithin facilitates emulsion formation. Polymeric
surface active or interfacial agents such as polysaccharide esters (e.g.,
starch palmitate) may be desirable to form a controlled surface layer. The
aqueous phase particles may be separated from the hydrophobic liquid
making fluid to provide a microparticulate polysaccharide/protein complex
having a controlled particle size. The particles may be heated in the
hydrophobic working liquid (e.g., to 90.degree.-105.degree. C.) to
stabilize the precipitated complex microparticles prior to separation from
the hydrophobic working liquid. Such heating may be carried out under
superatmospheric pressure to prevent water loss if desired.
It is important to avoid oxidation of the oil if recyclic use of the oil
phase is desired for commercial operation. The use of a nitrogen blanket,
and deaeration of the oil and the complex-generating solution are
preferred procedures in this regard. It may also be desirable to use high
stability oils.
The size of the fibers is constrained by the size of the emulsion droplets
in these methods. By controlling the size of the emulsion droplets, the
size of the fiber particles may be readily controlled. The energy
requirement for forming an emulsion is much lower than for
microfragmentation of preformed fibers, and accordingly, less work is
necessary to produce particles of a preselected volume through
emulsification of the aqueous fiber forming solution utilized in high
shear microfragmentation of the preformed fibers.
While aqueous polysaccharide/protein microparticulate dispersions may be
prepared utilizing high shear aqueous processing methods and hydrophobic
liquid emulsions, as previously described, it is also contemplated that
aqueous polysaccharide/protein complex dispersions may be provided by gas
atomization techniques. In accordance with such methods, an aqueous gas
atomization complex forming solution of a solubilized protein as
previously described, such as whey protein, casein, egg white protein,
vegetable protein or mixtures thereof, and an ionic polysaccharide, as
previously described, such as xanthan gum, carrageenan, gellan,
carboxymethyl cellulose, and mixtures thereof may be provided at a weight
ratio of protein/polysaccharide in the range of 2:1 to 15:1 (e.g., about
8:1). The aqueous gas atomization solution may desirably have a total
solids content of less than 10 weight percent (e.g., about 5 weight
percent) of the solution. The solution will be at a pH higher than that at
which precipitation of a protein/polysaccharide complex occurs. Because
the process may involve evaporation/concentration, the solution may
desirably be a "pre-cleaned" solution in which off-flavors have been
removed by prior precipitation, washing and redissolution of the protein
and polysaccharide components, as described hereinabove, or may be a
polysaccharide/protein solution containing a high quality protein
component such as an egg protein/caseinate blend which does not have
significant "off flavor". Subsequently, the gas atomization
protein/polysaccharide solution is atomized in an entraining gas to form
droplets having a predominant diameter of less than about 10 microns, and
preferably about 5 microns or less, and more preferably about 3 microns or
less.
The gas atomized droplets are desirably contacted with an acidic atmosphere
such as carbon dioxide, acetic acid and/or hydrochloric acid in gas form
to precipitate the protein/polysaccharide complex. The gas atomized
droplets may also be heated by contact with hot gas to evaporate at least
a portion of the water content of the droplets. One embodiment of the
process is illustrated in FIG. 19.
As shown in FIG. 19, a pre-cleaned or otherwise flavor-free
protein/polysaccharide solution 1902 such as a carrageenan/egg
white/sodium caseinate (solids weight ratio 1:4:4) at a pH of 6-7 and
having an initial solids content of 5 weight percent is atomized into a
drying tower 1904 by an atomizer or nebulizer 1906 in the form of a spray
of droplets 1908 having a diameter of less than 6 microns. The solution
1902 may be saturated with a gas such as nitrogen at high pressure prior
to atomization to assist droplet size reduction by sudden release of gas
from the solution upon atomization, and may contain an edible surface
active agent to reduce surface tension, also to facilitate droplet
formation.
In the drying tower 1904, the droplets 1908 are contacted by an
acid-containing gas 1910, in appropriate concentration and amount to
reduce the pH of the droplets to a pH at which precipitation occurs, which
is preferably at, or slightly above, the isoelectric point. The
temperature of the gas may be sufficiently high to denature the protein,
although cooler temperatures including ambient or lower temperatures may
be used if desired. The humidity of the gas may be controlled in an
appropriate manner (as by partial gas recycle or steam injection, etc.) to
control the amount of water evaporation from the droplets. The exhaust gas
stream 1912 may be cooled to condense moisture, heated and recycled.
Protective materials, such as sugars, starches, dextrins, etc., may be
used for higher levels of drying (below 65 weight percent water). It is
preferred, however, that the droplets 1908 be partially dried to a range
of from about 15 to about 25 weight percent solids, thereby
correspondingly reducing the size of the individual droplets. The
partially dried droplets may be collected as an aqueous dispersion 1914
after their brief encounter with the preferably high temperature
(90.degree.- 120.degree. C.) gas 1910 in the tower chamber, to provide an
aqueous dispersion. This acidic gas vapor treatment, in view of the high
surface area of the droplets, may partially remove any volatile odor or
taste components, if present. If desired, the droplets may be immediately
cooled by contact with the collected aqueous dispersion or collection
chamber walls to maintain the stability of the aqueous dispersion.
To obtain uniformly small droplet size, special attention should be given
to the atomizing methods and apparatus. Pneumatic atomizers typically use
compressed air (e.g., 30-100 psi or 200-700 kPa) and produce droplets in
the range of 5-10 microns in diameter. Rotary atomizers (spinning disks)
which are widely used in spray drying normally produce droplets in the
30-300 micrometer range. However, by utilizing high pressure gas streams
with pneumatic atomizers, by the application of ultrasonic atomizing
techniques in the 1.times.10.sup.6 to 1.times.10.sup.7 Hz frequency range
to pneumatic and very high speed rotary disk atomizers, and/or by
utilizing electrostatic atomizing techniques, uniformly small diameter
droplets may be readily produced. A pneumatic nozzle system 2000 is
schematically illustrated in FIG. 20. As shown in FIG. 20, a small conduit
2002 emits a stream 2004 of the protein/polysaccharide solution from which
individual droplets 2006 are formed, as shown, and subjected to contact
with high velocity acidic gas, which causes precipitation of the
protein/gum complex within the droplet. A heated gas stream 2012 from an
outer nozzle 2014 provides for water evaporation and denaturation of the
complex. Wide variation of process conditions may be controlled to provide
specific treatment of the small droplets formed. For example, the
protein/polysaccharide stream 2004 may be initially formed into droplets
by contact with a relatively cool high velocity air stream, and contacted
thereafter by a high temperature acidic gas stream. If the air stream
contains an acidic gas (e.g., CO.sub.2 and/or HCl) so that the
precipitation begins before droplet formation is complete, the protein/gum
complex precipitate will be oriented, and irregularly shaped, as shown in
magnified insert 2016. If contact with acidic gas occurs after droplet
formation is complete, the precipitation complex may be less oriented, as
shown in enlarged input 2018. The droplet formation may be carried out by
means of a high temperature gas (such as an air-steam mixture) to denature
the protein before, after or concomitantly with droplet formation, and
before, after or concomitantly with acidification. The droplets may be
heated to denature the protein/polysaccharide complex of the individual
drops and to remove at least a portion of the water content. Thus, for
example, the water content may be reduced so that the droplets are
approximately 80% by weight water, rather than the original 95-96% water.
The temperature of the droplets and the amount of drying may be controlled
by controlling the amount of humidity and temperature of the hot gas
(e.g., by heat exchange, heated air or steam) introduced into the
droplet/gas interaction chamber. The pressure in the chamber may be
approximately atmospheric pressure, but may be superatmospheric if desired
to heat the droplets to higher temperatures than 100.degree. C. for more
rapid protein denaturation, or may be subatmospheric if high evaporation
rates at low temperature are desired. Smaller droplets are, because of
their relatively larger surface area as compared to their mass,
increasingly subject to air flow conditions with decreasing size. This
property may be utilized to cause impaction of larger drops against a
multi-tiered surface or filter 2020 to remove larger drops from the final
dispersion to be produced, while permitting droplets of desired size to
pass through the filter. The parameter which is a measure of this inertial
effect may be defined by a dimensionless ratio Psi equal to the stopping
distance (e.g., the distance a drop will penetrate in still gas given an
initial velocity Vo divided by a spray or collector diameter.
Frozen Desserts--As indicated, frozen desserts incorporating
microfragmented ionic polysaccharide/protein complexes, such as the
preferred xanthan/protein complex dispersions, have particular utility.
Typically, in conventional frozen dessert formulations, the higher the fat
level in a frozen dessert, the more pleasing and appetizing is its texture
and flavor. For example, ice cream, which usually comprises at least about
10 percent of milk fat, typically has texture and flavor superior to the
texture and flavor of frozen desserts comprising low proportions of fat.
However, the higher the fat content of the frozen dessert, the higher is
the calorie content of the frozen dessert. Nutritious, low calorie, low
fat frozen desserts having desirable texture and flavor characteristics
similar to higher fat content desserts, and having substantial shelf and
flavor stability, together with a creamy texture may be provided in
accordance with the present disclosure. Such frozen desserts may comprise
from about 0 to about 10 percent of edible fat, from about 1 to about 10
percent of a microfragmented xanthan/protein complex dispersion (dry
basis), from about 1 to about 9 percent by weight of protein (dry basis,
not including the protein content of the xanthan/protein complex), from
about 10 to about 30 weight percent of a saccharide component comprising
one or more sugars, and from about 45 to about 80 percent water. Various
gums, stabilizers and emulsifiers, flavoring agents and flavoring food
components may also be included, in accordance with conventional practice.
In preparing such frozen desserts, a mix is prepared which comprises an
aqueous component, and optionally a fat component. The fat component
comprises less than about 10 percent of the mix, and may be any edible fat
which is firm but spreadable at room temperature, such as milk fat and/or
margarine fat. The fat component will desirably comprise at least about 1
percent of the mix, such as from about 2 to about 5 percent by weight,
unless it is desired to provide entirely fat-free frozen dessert products
having a creamy texture.
The aqueous component will ordinarily comprise water, protein and
sweetening agents and may also comprise stabilizers and flavoring
ingredients. The xanthan/protein component (and the optional fat
component, if utilized) may be thoroughly mixed with the other component,
and the mix may be homogenized to provide a thoroughly homogenized
composition which may then be subjected to freezing in a conventional
manner, as by a swept surface heat exchanger.
The mix may be packaged and hardened after discharge from the heat
exchanger to provide a low-fat frozen dessert having excellent creamy
texture and flavor together with reduced calorie content in a reduced fat
or fat-free composition.
Food Dressings--The microfragmented ionic polysaccharide/protein complex
dispersions, particularly including the preferred xanthan/protein complex
dispersions are also particularly useful as components of low oil or
oil-free dressings, such as salad dressings, viscous and pourable
dressings. Shelf stable acidic food dressings comprising xanthan/protein
complex dispersions are particularly desirable, comprising a blend of an
acidic aqueous fluid food dressing vehicle having a pH of less than about
4.1 and a creamy-textured xanthan/protein microfragment dispersion
component which retains its stability in the acidic food dressing vehicle.
The shelf-stable food composition will generally comprise from about 0.25
to about 30 percent by weight, and preferably from about 1 to about 10
percent by weight of the microfragmented xanthan/protein complex
dispersion (solids basis), 0 to about 50 percent and preferably less than
about 30 percent by weight of an edible oil or fat, and from about 50
percent to about 99.75 percent by weight, and preferably from about 90
percent to about 99 percent by weight of the aqueous fluid food dressing
vehicle, based on the total weight of the food dressing. Up to about 20
weight percent of other components, such as particulate food components,
may be included in the dressing.
The food dressing vehicle utilized in accordance with the present invention
will generally contain from about 20 to about 96 percent by weight of
water, and sufficient acidifying agent to provide the aqueous component of
the dressing vehicle with a pH of less than 4.1, and preferably in the
range of from about 2.75 to about 3.75. In accordance with conventional
food dressing manufacture, depending on the desired pH, the amount of
water in the dressing vehicle and the effect of additional components of
the food dressing, the acidifying agent which may include acetic acid or a
mixture of acetic and phosphoric acids, will generally be present in an
amount of from about 0.1 to about 3.5 weight percent based on the total
weight of the food dressing vehicle.
Also in accordance with conventional acid dressing manufacture, the food
dressing vehicle may contain up to about 20 weight percent of a bodying
agent such as gums, starch or other hydrocolloids and mixtures thereof,
from about 0 to about 5 percent salt, from about 0 to about 30 percent
sweetener, and from about 0 to about 15 percent spices and flavors, based
on the total weight of the food dressing vehicle. The food dressing
vehicle which may be utilized includes oils or oil-less dressings,
pourable or viscous dressings and emulsified or nonemulsified food
dressing products commonly used as an adjunct on salads, vegetables,
sandwiches and the like. Included within such classification are products
such as mayonnaise, salad dressing and French dressing, and imitations
thereof, as well as low calorie oil-less products, including condiments or
reduced calorie products, and other emulsified and nonemulsified
oil-containing products.
The oil, to the extent used in the dressing formulation, may be any of the
well known edible triglyceride oils derived from oil seeds, for example,
corn oil, soybean oil, safflower oil, cottonseed oil, etc., or mixtures
thereof. The sweetener used is typically sucrose. However, other
sweeteners such as dextrose, fructose, corn syrup solids and synthetic
sweeteners may also be utilized.
Any suitable emulsifying agent may be used in the salad dressing
compositions of the invention. In this connection, egg yolk solids,
protein, gum arabic, carob bean gum, guar gum, gum karaya, gum tragacanth,
carrageenan, pectin, propylene glycol esters of alginic acid, sodium
carboxymethyl-cellulose, polysorbates and mixtures thereof may be used as
emulsifying agents in accordance with conventional food dressing
manufacturing practices. The use of emulsifying agents is optional and
depends upon the particular type of emulsified oil being prepared.
Emulsifying agents, when used, may typically be present at levels of from
about 1 percent to about 10 percent, depending on the particular
emulsifying agent used.
A bodying agent may be used in the food dressing vehicle to provide desired
body or viscosity in accordance with conventional practice, in addition to
the xanthan/protein complex dispersion (which serves as a creamy
functional bodying agent). This bodying agent may be a starch paste or may
comprise an edible gum such as xanthan gum (as a bodying agent, not as
part of the molecularly intimate xanthan/protein complex), guar gum,
propylene glycol ester of alginic acid or the like. Starch, if used, may
typically be present at a level of from about 2 percent to about 10
percent. The edible gum will typically be present at lower levels to
provide desired body and texture.
Starch paste is generally used as a bodying agent in the preparation of
semisolid emulsified oil dressings, such as salad dressing, and may be
used in the preparation of pourable emulsified oil dressings, such as
French dressing. The starch may be utilized at a level of from about 1 to
about 10 percent by weight in semisolid dressings and at a level of from 0
percent to about 8 percent in pourable dressings. Any suitable starch
containing material may be used, and in this connection, any food starch,
whether modified, unmodified or pregelatinized, tapioca flour, potato
flour, wheat flour, rye flour, rice flour or mixtures thereof may be used
as a bodying agent in the preparation of food dressing vehicles.
Similarly, the bodying agent may comprise edible gums individually or in
combination, and the gums will usually provide the desired body and
texture at levels below those normally required when starch paste is used.
The gums, when used as a bodying agent, may typically be present at a
level of between about 0.05 percent and 2.5 percent. Various other
ingredients, such as spices and other flavoring agents, and preservatives
such as sorbic acid (including salts thereof) may also be included in
effective amounts.
The dressing vehicle may have an aqueous pH of about 4.1 or lower,
preferably in the range of from about 2.75 to about 3.75. Any suitable
edible acid or mixture of acid may be used to provide the desired level of
acidity in the emulsified dressing, with suitable edible acids including
lactic acid, citric acid, phosphoric acid, hydrochloric acid, and acetic
acid and mixtures thereof. Mixtures of acetic acid and phosphoric acid are
particularly preferred acidifying agents. The amount utilized to achieve a
desired pH will depend on a variety of factors known in the art including
the buffering capacity of protein components of the dressing.
The microfragmented xanthan/protein complex dispersion is an important
component of the food dressings, and may be blended with the other
dressing ingredients in the form of a hydrated aqueous dispersion. Such
hydrated aqueous xanthan/protein microfragmented complex dispersions may
typically comprise from about 55 to about 99 percent water, and from about
1 to about 45 percent by weight complexed xanthan gum and protein. The
xanthan/protein complex dispersion may also be formed directly in the
aqueous vehicle utilized in the dressing preparation.
Such dressings may also comprise fiber agglomerates or other large fibers
of xanthan/protein fiber complexes, for example, having a mass of less
than about 2 grams, and more preferably from about 0.02 grams to about 1.5
grams. Such large fibers and fiber agglomerates are not considered herein
to be included in the complex dispersion component.
Confections--Various aspects of the present disclosure are also directed to
reduced calorie confectionery having increased nutritional balance,
reduced calorie content, and/or novel organoleptic and mouthfeel
characteristics. The microfragmented ionic polysaccharide/protein complex
dispersions, particularly including the preferred xanthan/protein complex
dispersions, are important components of novel low fat, or no fat
confections having desirable organoleptic characteristics. Confections are
characteristically comprised primarily of sugars. By sugars is meant
nutritive sugars such as nutritive mono, di and polysaccharides such as
sucrose, dextrose, levulose and starch syrups such as corn syrups of
varying composition including dextrin, maltose and dextrose, and
non-nutritive sweeteners such as polyglucose, xylitol, as well as
artificial sweetener agents such as saccharine and aspartame. Confection
products utilizing microfragmented xanthan/protein complex dispersions may
be prepared in accordance with the present invention which generally
comprise:
______________________________________
Ingredients Weight Percent
______________________________________
Microfragmented xanthan/protein
.5-10%
complex dispersion (solids basis)
Water 2-20%
Sugar 10-90%
Fat 0-40%
Gums & Stabilizers 0-10%
(other than xanthan gum complexed
with protein in xanthan/protein
microfragment complex)
Flavoring 0-10%
Starch 0-15%
Protein (other than 0-20%
xanthan/protein complex)
______________________________________
Confection products may be classified into two general groups depending
upon the physical state in which the sugar is present. The crystalline
solid phase is observed in fondant and the liquid or monocrystalline
phase, which is sometimes referred to as amorphous state, is found in hard
candy, which, like glass, is a highly supercooled liquid. Components such
as corn syrup, fats, invert sugar, nonfat milk solids and gums influence
the physical characteristics of the finished confection, as do the
processing conditions of manufacture, such as cooking time and temperature
and method of handling after removal from the cooker. Because of the wide
variety of confections made possible by regulating the proportion of these
two phases-- solid and liquid-- of sugar, confections may also be further
classified as hard candy, fondant, fudge, caramels, marshmallows, nougat,
sugar lozenges, starch jellies, sweet chocolate products and bonbons. The
inclusion of the microfragmented xanthan/protein complex dispersion
component in the confection blend prior to cooking may also influence the
properties of the resulting confection product.
Fudge is a grained confection composed of water, sucrose and/or levulose,
and/or dextrose, and/or maltose, and/or dextrins along with satisfactory
flavoring materials and whole milk or milk solids not fat with or without
added cream and/or dairy butter and/or satisfactory fat. Caramels are
confections composed of water, sucrose, levulose, dextrose and/or maltose
and/or dextrins along with whole milk or non-fat milk solids, as they
appear in whole milk and a satisfactory fat with or without the addition
of satisfactory colors and/or flavors. The organoleptic properties,
texture and nutritional balance of fudges and caramels may be tailored
through the incorporation of up to about 10 weight percent xanthan/protein
microfragments in the confection.
Aerated confections are confections in which a substantial amount of air is
permanently incorporated in the formed confection. Marshmallows are an
aerated confection whose consistency may be short or grained, elastic and
chewy or of a semi-liquid character.
As described in U.S. Pat. Nos. 2,847,311, 3,062,611, 3,220,8953 and
3,607,309, marshmallows and similar confections are conventionally
manufactured by extruding a heated, aerated confection blend to form
multiple strands. The extruded strands may be coated with starch, powdered
sugar or mixtures thereof to prevent sticking of the strands to each
other, and cut transversely to their longitudinal axes to form firm
textured confection products of desired size, having a density in the
range of from about 0.25 to about 0.39 grams per cubic centimeter. By
including up to 10 weight percent of xanthan/protein complex
microfragments in the confection mix prior to operation, aerated
confections may be provided which have substantially improved nutritional
balance.
The food commonly and usually known as "Milk Chocolate" or "Milk Chocolate
Coating" is the solid or semi-plastic food composed basically of chocolate
liquor intimately mixed and ground with milk solids and one or more of the
sugar ingredients (cane or beet sugar, partially refined cane sugar,
anhydrous dextrose or dried corn syrup). Milk chocolate candy
incorporating up to about 10 weight percent of a microfragmented
xanthan/protein complex dispersion (solids basis), may be provided which
has significantly reduced calorie content.
Comminuted Meat and Meat Analog Products--Processed comminuted meat
products such as hot dogs and luncheon meats are conventionally prepared
in relatively large, unsliced bulk form such as sausages, hot dogs or
loaves, or in the form of slices. Such processed meat products may be
manufactured by preparing an emulsion of the desired processed meat
constituents, together with flavoring agents or preservatives, forming the
resulting emulsion in a desired shape such as a cylindrical shape, and
heating the emulsion to at least an elevated, coagulation temperature to
solidify or pasteurized the meat mass. While heat settable meat emulsions
typically utilize natural meat components, meat analog products which
utilize a heat setting vegetable protein are also known.
Such comminuted meat products typically include relatively high levels of
fat to provide a desired texture and organoleptic properties. In
accordance with the present disclosure, reduced fat products may be
prepared which include microfragmented ionic polysaccharide/protein
complexes in place of all or a part of the fat component. Such complexes
may be used in heat-settable meat emulsions. By "heat-settable" is meant
that the meat product emulsion initially is a viscous, flowable form, is
transformed into a form stable condition by heating the emulsion to a
temperature of at least about 120.degree. F. Desirably, "heat-settable"
meat product emulsions include a heat coagulatable protein component which
provides the desired product form stability upon heat coagulation of the
protein component. However, other heat settable compositions, such as
those which include heat activated gel-forming agents such as
hydrocolloids or hydrocolloid/protein blends, which form a firm,
form-stable matrix upon heating, may be utilized.
The meat emulsion may desirably comprise at least about 5 percent by weight
protein and preferably in the range of from about 7 to about 16 weight
percent of meat or vegetable protein, based on the total weight of the
meat emulsion. The meat product emulsion may further desirably comprise
from about 0 to about 25 weight percent animal or vegetable fat, and
preferably in the range of from about 5 to about 20 percent fat by weight,
based on the total weight of the meat emulsion product. The meat emulsion
will further comprise from about 2 to about 30 weight percent (solids
basis) of a microfragmented ionic polysaccharide/protein complex as
previously described. The meat emulsion product may further comprise
additional components including salt, sweeteners, extenders and binders,
protective and preservation agents such as sodium ascorbate, sodium
erythorbate and sodium nitrite. Such additional processed meat components
may be provided in accordance with conventional practice. It may also
comprise from about 25 to about 65 weight percent total solids and from
about 35 to about 75 weight percent of water, based on the total weight
of the meat product emulsion. The heat-setting meat emulsion composition
may desirably include a heat-activated starch which renders the emulsion
non-syneresing.
The type of meat components which may be utilized in the meat emulsion of
the present invention include beef, pork, poultry, such as chicken and
turkey, fish protein such as surimi, vegetable proteins such as soy
protein and cottonseed protein, dairy protein such as milk solids and
microbial protein such as yeast protein. The heat-setting meat emulsion
composition may be prepared by grinding, chopping and emulsifying the
component ingredients to provide a substantially homogeneous meat emulsion
product.
Baked Goods--Reduced calorie baked goods, and more particularly, low fat
baked goods having desirable texture and organoleptic characteristics may
be prepared using microfragmented or microparticulated ionic
polysaccharide/protein complexes as described herein. Baked goods
typically utilize substantial quantities of triglycerides to develop
texture and organoleptic properties. However, triglycerides such as butter
and shortenings such as partially hydrogenated vegetable oils have high
caloric content. Moreover, consumers, for various reasons, may wish to
reduce their triglyceride intake. Microfragmented anisotropic
xanthan/protein complex dispersion containing the hydrated xanthan/protein
complex microfragments in an aqueous dispersion are particularly desirable
components of such baked goods, such as sweet dough, danish dough, puff
pastry, and leavened products such as cake mixes, and less leavened
products such as brownies. Desirably, the microfragmented ionic
polysaccharide dispersion will be utilized at a level of from about 1
percent to about 10 percent solids basis, in full or partial replacement
for the shortening component.
Sweet dough is that product, which is made from solid sponge, liquid sponge
or straight dough, but which receives no added fat (or material similar)
for roll-in purposes. Typically, texture is relatively even and round in
appearance. Danish dough is that dough which receives part of its fat as a
roll-in which when baked, exhibits the characteristic flake typical of
Danish. Texture differs in as much as the cellular structure is more
elongated and uneven. The base dough may also be made from solid sponge,
liquid sponge or straight dough. Puff pastry is also layered or laminated
but without the yeast leavening relying on the dough/fat interaction to
produce the desired lift and flake.
Improved baked goods products such as sweet breads, sweet rolls, buns,
coffee cakes, donuts and danish pastry, as well as cakes, pastries, pie
shells, cookies, breads, icings, toppings and fillings may be made having
reduced fat content.
Pastry products such as sweet dough, danish dough and puff pastry products
with reduced fat may be provided. It is also an object to provide
conventional products having improvement in quality without deletion of
part or all of the conventional shortening.
Conventional sweet dough products are yeast leavened baked goods including,
but not limited to sweet breads, sweet rolls, buns, coffee cakes,
doughnuts and danish pastry where a portion of the fat is rolled in. Also
puff pastry, where yeast is not utilized as a leavening agent.
Improved low fat baked goods products utilizing ionic polysaccharide
complex dispersions include, sweet dough, danish dough products, cakes,
pie shells, cookies, breads, icings, toppings and fillings.
Such methods may be used to produce a wide variety of aqueous
protein/polysaccharide dispersions in an economical manner.
Having generally described various aspects of the present invention, the
invention will now be more particularly described with reference to the
following specific Examples.
EXAMPLE 1
A series of anisotropic xanthan/protein complex macro fibers was prepared,
which were subsequently processed under high shear conditions to form
respective microfragmented dispersions.
A first batch of xanthan/protein complex fibers was prepared as follows.
Twenty-five grams of whey protein concentrate "WPC" (protein=35.47%;
lactose=50.1%; moisture=5.03%; fat=3.15%; ash=6.93%, by weight), and
twenty-five grams of dried egg albumen (Kraft dried egg whites) were
suspended in 2800 milliliters of distilled water in a Waring blender (with
stirring) to provide a protein solution. To the protein solution was added
8.33 grams of xanthan gum (Keltrol Xanthan Gum from Kelco Chemical Co.)
with stirring in the same Waring blender, and the mixture was stirred for
5 minutes at 22.degree. C. to form a fiber generating solution. The fiber
generating solution was acidified with 35 milliliters of 1 molar
hydrochloric acid with stirring. The fibers were collected and washed with
cold water. The washed fibers were boiled for 5 minutes and drain-dried
after washing. The fibers were very white and firm. They had a very bland
taste. The wet fibers were frozen and stored for approximately two years.
The fibers were then removed from frozen storage, thawed and freeze dried
to a total moisture content of about 5 percent by weight. The dried fibers
were ground by centrifugal grinder (Brinkmann Pulverizer) using a 0.2
millimeter screen and a high speed setting to provide dried particles of
about 100 microns in size. The ground powder was reconstituted with water
to form a ten weight suspension in distilled water. The suspension was
subjected to high shear by being conducted through a high shear hydroshear
device (Microfluidizer model 110Y sold by Biotechnology Development
Corporation of Newton Upper Falls, Mass.) at a process input pressure of
about 13,500-18,000 psi. The suspension was passed through the high shear
microfluidizer five times, with product samples being taken after each
pass. The temperature rise upon passage through the microfluidizer is
approximately 1.7 degrees centigrade per one thousand pounds psi input
pressure, providing a temperature rise of about 30.degree. C. upon passage
through the device. The product was initially at ambient temperature, and
despite limited ambient cooling between passes, was raised over the course
of the five passes to a temperature of about 140.degree. F.
The microfluidized xanthan/protein complex was acidified to pH 4.0 with 1
molar hydrochloric acid and then centrifuged at 4,100 times normal gravity
(".times.g") and 25.degree. C. for 20 minutes. The centrifuged pellets
were recovered for subsequent analysis and incorporation into various
product formulations, and were evaluated organoleptically. It was found
that these microfluidized xanthan/protein complexes were smooth, creamy
and had a fatty mouthfeel. The "concentrated" microfragmented
xanthan/protein dispersion had a solids content of 24 percent by weight.
EXAMPLE 2
Xanthan/protein complex fibers were made as illustrated in FIG. 1.
Referring to FIG. 1, eight gallon batches of protein/gum slurry (2%
solids; 1/8 xanthan; 7/16 egg white; 7/16 whey protein concentrate by
weight, based on total solids weight of xanthan gum, egg white and whey
protein concentrate) were mixed in the Tri-blender at 110.degree. F. and
transferred to the holding tank (It is noted that the temperatures may
desirably be reduced to 60.degree.-70.degree. F.) Xanthan/protein fibers
were continuously formed by acidifying a stream of the xanthan/protein
solution in the holding tube.
The flow rate through the holding tube and Moyno pump was 8 lbs/minute and
the acid rate was adjusted to obtain a pH of 3.0-3.5 at the discharge
stream from the Moyno pump. The Moyno pump screw rate was 160 rpm.
Five gallon batches were collected from the Moyno pump, and the whey was
separated from the formed fibers by passing through screens. The fibers
collected from 30-40 gallons of processed slurry were then placed in the
Groen kettle and heated in 10 gallons of water to a temperature below
boiling temperature. The heated fibers were washed with cold process
water, drained and convection dried.
The dried fibers were then suspended in water to form a 5 weight percent
(solids basis) slurry which was subjected to high shear microfragmentation
by recirculating treatment in a high shear hydroshear apparatus (Model
110Y sold by Biotechnology Development Corporation of Newton Upper Falls,
Mass.) for 40 minutes at 110.degree. F. at an input pressure of
13,500-18,000 psig. (It is noted that this pressure may desirably be
reduced to about 15,000 psig.) The microfragmented material was adjusted
to pH 4.0 and centrifuged at 16,000.times.g for 20 minutes. The solids
content of the centrifuged product following this procedure was 15-16%.
The material was a white, creamy, thick paste.
EXAMPLE 3
Xanthan/protein complex fibers were made by a continuous process in a
manner similar to Example 2 and generally as illustrated in FIG. 1, except
that the formed fibers were boiled in water, and were not convection dried
prior to high shear microfragmentation processing.
Referring to FIG. 1, eight gallon batches of protein-gum slurry (2% solids;
1/8 xanthan; 7/16 egg white/7/16 whey protein concentrate by weight, based
on total solids weight of xanthan gum, egg white and whey protein
concentrate) were mixed in the Tri-blender at 110.degree. F. and
transferred to the holding tank (It is noted that this temperature may
desirably be reduced to 60.degree.-70.degree. F.) Xanthan/protein fibers
were continuously formed by acidifying a stream of the xanthan/protein
solution in the holding tube.
The flow rate through the holding tube and Moyno pump was 8 lbs/min and the
acid rate was adjusted to obtain a pH of 3.0-3.5 at the discharge stream
from the Moyno pump. The Moyno pump screw rate was 160 rpm.
Five gallon batches were collected from the Moyno pump and the whey was
separated from the formed fibers by passing through screens.
The fibers collected from 30-40 gallons of processed slurry are then placed
in the Groen kettle and boiled in 10 gallons of water (5 minutes at
212.degree. F.).
The cooked fibers were washed with cold process water, drained and placed
in cooler (35.degree. C.) before use.
The fibers are then microfluidized by treatment in a (Model 110Y sold by
Biotechnology Development Corporation of Newton Upper Falls, Mass.) for 40
minutes at 110.degree. F. an input pressure of 13,500-18,000 psig. The
fluidized material was adjusted to pH 4.0 and centrifuged at 16000.times.g
for 20 minutes. The manufacturing procedure was substantially duplicated
to provide another lot of the microfragmented dispersion, which was
designated "Lot 2". The solids content of the centrifuged product
following this procedure was 13-16%. This product was designated "Lot 1".
The material, which was a white, creamy thick paste, was subjected to
various analyses, and was also incorporated in a variety of food products,
as will be further described.
EXAMPLE 4
The aqueous, microfragmented xanthan/protein complex dispersions of
Examples 1, Example 2 and Example 3 were characterized by various
laboratory analyses.
The protein content of the respective microfragment dispersions was
analyzed by Lowry method using bovine serum albumen standard curve.
Xanthan content was determined by phenol/sulfuric acid method for hexose,
using a xanthan standard curve. Calculated values were corrected for
contributions of xanthan and protein to Lowry and phenol/sulfuric acid
assays. The xanthan and protein composition of the microfragmented
particles was determined to be as follows:
______________________________________
Composition of Microfragments
Sample Protein/Xanthan Ratio
______________________________________
Example 1 2.4 to 1
Example 2 2.3 to 1
Example 3 - (Lot 1)
2.5 to 1
Example 3 - (Lot 2)
2.6 to 1
______________________________________
The amount of denaturation of the protein of the xanthan/protein
microfragmented particles of the respective dispersions was determined by
polyacrylamide gel electrophoresis in sodium dodecyl sulfate buffers
(SDS-PAGE) in the presence or absence of a reducing agent, dithiothreitol
(.+-.DTT), which indicates the amount of crosslinked denatured protein.
Accordingly, it will be appreciated that the total denaturation may be
higher than the amounts determined by this technique. The measured percent
of denaturation for the dilute microfragmented dispersions was as follows:
______________________________________
Denaturation
Egg White Whey Protein Total
Sample (Ovalbumin) (B-Lactoglobulin)
Protein
______________________________________
Example 1
93% 74% 86%
Example 2
83% 43% 65%
Ex. 3 - Lot 1
94% 82% 91%
Ex. 3 - Lot 2
93% 74% 85%
______________________________________
Differential scanning calorimetry (DSC) was also carried out on the
products. DSC analysis indicates no detectable native structure the
products of Examples 1 or 3 (FlG. 7). However, the product of Example 2
(FIG. 6) was found to have a significant amount of undenatured whey
protein by DSC, confirming the SDS-PAGE data (See FIGS. 6-8).
The microfragmented dispersion of Examples 1, 2 and 3 pelleted easily
during low-speed centrifugation (1600.times.G for 10 minutes) at pH 4.0
and below. At pH 5.0 and above, a substantial (60-70%) portion remains
suspended. These results indicate that flocculation occurs at low pH. This
is substantiated by (SEM) scanning electron microscopy (See FIGS. 9 and
10) in which the complex is dispersed at pH 5.5, but aggregated at pH 4.0.
The titration curve for this phenomenon corresponds generally to the
titration curve of the proteins used in the preparation of the
microfragmented dispersions. The midpoint of the titration curve occurs at
pH 4.8 (see FIG. 11).
The addition of salt has the same effect as raising the pH (see FIG. 12).
The flocculation is rapid, reversible, and may be due to electrostatic
interaction between positively charged regions of the protein on one
microfragment and negatively charged xanthan on another microfragment.
Heat stability of the microfragment dispersions of Examples 1, 2 and 3 was
determined by measuring viscosity before and after subjecting the
respective microfragment dispersion to 5 minutes on a boiling water bath.
All preparations increased in viscosity after boiling; samples with higher
original viscosity turned to gel. Lower viscosity samples seemed more heat
stable.
Samples were tested using a Haake Rotovisco (Example 1 and Example 2) and
using a Brookfield Viscometer (Examples 1-3).
______________________________________
Haake Rotovisco Data
Viscosity at Shear Rate 10
Sample Solids Before Boiling
After Boiling
______________________________________
Example 1 7.4% 115 cps 181 cps
not gelled
Example 1 7.4% 680 cps 1850 cps
gelled
______________________________________
Brookfield Data*
Yield Value
Viscosity
Sample Solids Before After Before
After
______________________________________
Example 1
12.4% n.d. 3.4 n.d. 2.2 ng
Example 1
17.7% 1.6 51 1.3 7.3 g
Ex 3, Lot 1
11.05% 2.4 32 2.8 16 g
EX 3, Lot 2
13.4% 9.1 70 10.5 21 g
______________________________________
(ng = not gelled g = gel)?
*The numbers represent the average Brookfield reading using a small sampl
adapter equipped with Tbar spindle F. A helipath stand was used for all
measurements. Yield is the initial reading, viscosity is after 5 minutes.
Before and after refer to the boiling step.
Light microscopy of the microfragmented dispersion of Example 1, stained
with methylene blue, was carried out, which indicated fibrous material.
The fibers of Example 1 before microfragmentation were up to 100
micrometers in the longest dimension. After successive passes through the
microfluidizer, fibers are reduced in size to below 5 micrometers in their
largest dimension. After the ninth pass, most of the particles are less
than 1 micrometer in their largest dimension. The fibrous nature of the
particles is still evident after 9 passes.
Transmission electron microscopy (TEM) of the microfragmented dispersion of
Example 1 before microfragmentation shows fibers are composed of strands
of small globules (ca. 20 nm) oriented in chains about 120 nm in diameter.
The fibers appear as tangled masses of these strands, some of which have
parallel orientation. The small globules are possibly crosslinked
aggregates of denatured protein (continuing ca. 10-30 individual protein
molecules). The alignment of the globules is presumably along a backbone
of xanthan molecules (see FIG. 3). The substructure of denatured protein
globules is evident and the orientation may well be around fragments of
xanthan molecules (see FIG. 3a).
Transmission electron microscopy of the dispersion of Example 1 after
microfragmentation shows small isolated fragments of fibers composed of
the same type of globules described above. Many are oriented in chains
which have the diameter of one globule, others are in thicker chains or
clumps. The substructure of denatured protein globules is evident and the
orientation may well be around fragments of xanthan molecules (see FIG.
3b).
Scanning electron microscopy (SEM) of the materials of Example 1 shows
irregular shaped particles decreasing in size with successive passes
through the microfluidizer. After 9 passes, the particles are 1-3
micrometers across with a "hairy" surface formed by projecting extremely
fine filaments (smaller particles would not have been retained in these
preparations). It is theorized that the fiber filaments may comprise
xanthan filaments which may or may not be associated with protein. It is
further theorized that, based on the stability studies, that above about
pH 4.8, the negatively charged hairs might keep the particles from
interacting, and provide high volume viscosity and lubricity properties.
Below pH 4.8 the hairs could collapse against the particles, allowing
closer association of the particles and reversible aggregation due to
electrostatic interaction (see FIG. 4a).
Examination of the material of Example 3 after the Pentax homogenizer but
before microfragmentation shows large fibrous masses which seem to have
the same hairy exterior seen in the material of Example 1. The pieces are
more fibrous, and less like the irregular particles of Example 1, which
may reflect the fact that the product of Example 3 was never dried. Upon
microfragmentation, the material of Example 3 formed very small
(submicron) particles.
The xanthan/protein complex microfragmented dispersions of Examples 1 and 3
were utilized in the preparation of novel ice cream, pourable dressing,
mayonnaise, spreads, barbecue sauces, dip, sour cream, analog cheese and
cream cheese products, which will be described in the following examples.
EXAMPLE 5
Light Soft Processed Cream Cheese Product
A reduced calorie, reduced-fat, processed cream cheese type product was
prepared utilizing the microfragmented anisotropic xanthan/protein complex
dispersion of Example 3, run 2, containing the hydrated xanthan/protein
complex microfragments in aqueous dispersion, and having a solids content
of 13.0 weight percent, based on the total weight of the dispersion. In
preparing the cream cheese type product, the following ingredients were
used to prepare a cultured dressing:
______________________________________
Ingredients Weight
(Sub A) Percent Amount
______________________________________
Water 63.33 5.33 lbs
Condensed Skim Milk
36.67 3.08 lbs
Lactic culture -- 4.50 milliliters
______________________________________
In preparing the cultured dressing (Sub A), the water and condensed skim
milk were combined with moderate agitation in a conical vat pasteurizer.
After the ingredients were thoroughly combined, the mixture was batch
pasteurized at 180.degree. F. for 5 minutes. The pasteurized dressing base
produced by pasteurizing the ingredient blend was cooled to 72.degree. F.
and inoculated with the lactic culture. The lactic culture was thoroughly
dispersed into the dressing base with agitation. The inoculated dressing
was was incubated at 72.degree.-76.degree. F. for 18 hours until a pH of
4.30 was obtained. The coagulum was broken by agitating for 15 minutes by
hand with a milk can stirrer. The cultured dressing base was then combined
with the following components, to form the finished product:
______________________________________
Ingredients Weight
(Final) Percent Amount
______________________________________
Cream cheese curd 49.50 12.71 lbs
Cultured Dressing (Sub A)
32.75 8.41 lbs
Microfragmented anisotropic
xanthan/protein
dispersion of Example 3
16.75 4.30 lbs
Salt 0.75 0.19 lbs
Vegetable Gum 0.25 0.06 lbs
______________________________________
The cultured dressing (Sub A) was reheated to 175.degree. F. in a conical
vat pasteurizer with slow agitation. The hot (175.degree. F.) cultured
dressing was blended with hot (160.degree. F.) cream cheese curd in a
Pfaudler-type blender using agitation and recirculation. To this
dressing-cream cheese blend was added the salt, vegetable gum and
microfragmented anisotropic xanthan/protein dispersion of Example 3, while
maintaining agitation and recirculation. When all the ingredients were
thoroughly blended, the product was homogenized at 2000 psi single stage.
The finished product was hand-filled into standard soft cream cheese
packaging.
The finished processed cream cheese-type product had approximately half the
fat of a conventional cream cheese. This product had a calorie content of
62 calories per one ounce serving, as compared with a calorie content of
96 calories per one ounce serving for conventional cream cheese. The
reduced calorie product had a smooth mouthfeel, and a slightly more
viscous body than a conventional soft-style cream cheese.
Processed cream cheese-type products containing a microfragmented
anisotropic xanthan/protein complex dispersion having the functionality
(e.g., softer body) of soft cream cheese may be readily prepared by
utilizing a microfragmented xanthan/protein complex dispersion starting
ingredient having a lower solids content in preparing the product.
An even lower-calorie, nutritious imitation sour cream dip product was
prepared by preparing a lower calorie Dip Base (Sub D) utilizing the
imitation sour cream (Sub C) component as previously described, without
any sour cream dairy component:
______________________________________
Ingredients Weight
(Sub D) Percent Amount
______________________________________
Sour Cream 46.25 3100 gr.
Imitation Sour Cream (Sub C)
46.25 3100 gr.
Water/Condensate 6.99 469 gr.
Gelatin 0.33 22 gr.
Vegetable Gum 0.11 7 gr.
Monostearin 0.07 5 gr.
______________________________________
All of the above lower calorie Dip Base (Sub D) ingredients were thoroughly
combined by agitation and recirculation in a Pfaudler-type mixer. The
combined (Sub A) ingredients were heated to 165.degree. F. with steam
injection, while maintaining agitation and recirculation. The heated
ingredients were homogenized at 2500 psi. The homogenized lower calorie
Dip Base was combined with the condiment (Sub B) component and waxy maize
starch, as previously described, in the following proportions:
______________________________________
Ingredients Weight
(Final) Percent Amount
______________________________________
Dip Base (Sub D) 81.13 2101 gr.
Condiments (Sub B) 17.21 446 gr.
Modified Waxy Maize Starch
1.66 43 gr.
______________________________________
In preparing the finished lower calorie dip product, the dip base (Sub D),
condiments (Sub B) and the modified waxy maize starch were combined by
hand with moderate agitation. The combined ingredients were heated with
jacket heat to 165.degree. F. while maintaining moderate agitation. The
finished product was hand-filled into standard dip packaging.
The finished imitation sour cream dip product had approximately half the
fat of a conventional sour cream-based dip. The product had a calorie
content of 35 calories per 28.35 gram serving, as compared with a calorie
content of 50 calories per 28.35 gram serving for a conventional sour
cream-based dip. The reduced calorie product had a smooth mouthfeel, and
the body was slightly firmer and more rigid then a conventional sour
cream-based dip.
EXAMPLE 6
Low-Fat Spread
A low-fat spread product was prepared using the microfragmented anisotropic
xanthan/protein complex dispersion of Example 3, lot 1, and having a
solids content of 16.2 weight percent, based on the total weight of the
dispersion. In preparing the low-fat spread product, the following
ingredients were used.
______________________________________
Weight
Ingredients Percent
______________________________________
Soybean oil 27.796
emulsifier mix 0.900
water salt mix (Sub B)
24.469
color 0.089
flavor 0.004
xanthan/protein dispersion
46.742
______________________________________
Sub B=water--89.350%; salt--10.217%; sorbate--0.409%; EDTA--0.024%
In preparing the spread, the oil was heated to 127.degree. F. A portion of
the oil was combined with the emulsifiers monoglyceride-90% and unbleached
soybean lecithin and then heated to 140.degree. F. while stirring with a
magnetic stirrer. This portion was combined with the remaining oil in a 1
gallon churn. Color (mixture of Vitamin A and beta carotene) was added to
this oil blend and stirred as before.
Water-salt mix (Sub B) (46.degree. F.) was slowly added (total addition
time was about 3 minutes) to the oil mixture while stirring to form an oil
continuous emulsion. The initial speed was increased from 400 to 800 rpm
during the addition. The microfragmented anisotropic xanthan/protein
complex dispersion was then added in small portions to the above emulsion.
During the course of this addition, the stirring speed was increased from
800 rpm to about 1500 rpm. Flavors were then combined with the above
mixture. The final temperature of the mixture was 66.degree. F.
The mixture was then pumped through a scraped-surface heat exchanger which
consists of a rotor having two stainless steel blades scraping the inner
surface of a cylinder, the outer surface of which is cooled by circulating
Freon-12. The rotor was rotating at the rate of about 700 rpm and the
product pumping rate was adjusted to give an exit temperature between
50.dbd. F. The product was filled into 2 oz. cups and stored at 45.degree.
F.
The low-fat spread prepared as above was compared to a 30% fat control
without the microfragmented xanthan/protein complex dispersion. The
xanthan/protein complex fragment-containing product had a softer, smoother
and creamier body compared to the control. In addition, the
microfragmented xanthan/protein dispersion-containing product did not have
the wax-like mouthfeel of the control, but had different melt
characteristics from the control and had full-bodied texture.
The microfragmented dispersion-containing product was examined with Light
Microscopy on thin smears of the product. A small amount of fresh material
was placed on a glass slide and then smeared using a second slide to give
different thicknesses of the smear. Care was taken to ensure that there
was minimal "working on the sample". The slide was then placed on a cold
metal block and stained using 2% Osmium Tetroxide solution and/or 2%
methylene blue solution in 1% borax. The microscopic examination showed
the oil and the microfragmented dispersion were interlaced throughout the
sample with some oil droplets entirely surrounded by the microfragmented
dispersion. Some water droplets could be seen within the oil. The
microfragmented complex could readily be seen within these channels.
EXAMPLE 7
Analog Cheese Loaf
A reduced fat, reduced calorie analog cheese loaf was prepared utilizing
the microfragmented anisotropic xanthan/protein complex dispersion of
Example 3, lot 2 containing the hydrated xanthan/protein complex
microfragments in aqueous dispersion and having solids content of 13
weight percent, based on the total weight of the dispersion. In preparing
the reduced fat, reduced calorie analog loaf, the following ingredients
were utilized:
______________________________________
Weight
Ingredients Percent
______________________________________
Water 45.75
Shortening 11.50
Acid Casein 21.00
Microfragmented anisotropic
11.50
xanthan/protein dispersion
salt 0.70
modified stabilized 5.8
waxy maize starch
Tricalcium Phosphate
1.50
Disodium Phosphate 2.00
Sorbic Acid 0.20
Color 0.05
______________________________________
In preparing the analog cheese loaf, the color, shortening and acid casein
were blended in a Hobart mixer at the lowest speed (Hobart N-50 of the
Hobart Mfg. Co.). After mixing these ingredients, the microfragmented
anisotropic xanthan/protein complex dispersion was added and blended under
minimum agitation until ingredients were thoroughly mixed. The modified
stabilized waxy maize starch was slowly added to the analog blend while
mixing at low speed. After all the starch was mixed in, the water was
slowly added to the analog blend while mixing at low speed. After all the
starch was mixed in, the water was slowly added under minimum continuous
agitation. The analog cheese blend, tricalcium phosphate, disodium
phosphate and sorbic acid were put into a Kustner cooker (Model
.22I.211.110, Kustner, Geneva, Switzerland) and cooked by steam injection
to 168.degree. F. for four minutes.
The finished product contained approximately half the fat content of the
cheese analog control product. The product had a calorie content of 58
calories per one ounce serving, as compared with a calorie content of 86
calories per one ounce serving for the cheese analog control product. The
reduced calorie, reduced fat product had a softer body and texture, but a
similar slick mouthfeel compared to a control analog product. The reduced
calorie product and control had similar melting properties.
Cheese analog products containing a microfragmented anisotropic
xanthan/protein complex dispersion having a body and texture similar to
control product may be prepared by utilizing a microfragmented
xanthan/protein complex dispersion to replace a portion of the fat while
adding a gelling polysaccharide to firm the texture.
EXAMPLE 8
Pasteurized Process American Cheese Product
A reduced calorie, reduced fat Pasteurized Process American Cheese Product
was prepared utilizing the microfragmented anisotropic xanthan/protein
complex dispersion of Example 3, run 2, containing the hydrated
xanthan/protein complex microfragments in aqueous dispersion and having
solids content of 16.0 weight percent, based on the total weight of the
dispersion. In preparing the new reduced fat cheese product, the following
ingredients were utilized:
______________________________________
Weight Weight
Ingredients Percent in Lbs
______________________________________
Skim milk cheese 30.50 9.150
Nonfat dry milk 1.90 0.570
Aged cheddar cheese 15.00 4.500
Color (0.04) (0.012)
Sodium Citrate Duohydrate
2.25 0.675
Disodium Phosphate Duohydrate
0.40 0.120
Sorbic Acid 0.20 0.060
Water 0.90 0.270
Steam condensate 8.35 2.505
Enzyme modified cheese
2.00 0.600
Microfragmented anisotropic
30.00 9.000
xanthan protein dispersion
Whey Powder 5.00 1.500
Whey Protein Concentrate
2.00 0.600
Sodium Chloride 1.50 0.450
100.00 30.000
______________________________________
*The coloring is not considered part of the weight percent.
To produce the cheese product, the ground skim milk cheese was blended with
the nonfat dry milk in a Hobart Mixer (Model AS-200), operating at the low
speed setting. This mixture and the other 6 ingredients above the steam
condensate were placed in a Damrow laboratory cheese cooker (40 lb.
capacity).
Direct steam and mixing (0.5 speed setting) were applied to these
ingredients. The enzyme modified cheese was added to the first ingredients
at a temperature of about 100.degree. F. The microfragmented microfragment
xanthan/protein complex dispersion of Example 3 was added to the cooker at
about 120.degree.-150.degree. F. and a preblended mixture of the whey
powder, whey protein concentrate (dry powder) and sodium chloride was
gradually poured into the cooker at about 160.degree. F. The steam heating
was continued to 175.degree. F. and the mixing was continued for about 4
more minutes (after 175.degree. F. had been reached) at which time the
hot, homogeneous, cheese product was smooth. It was packaged and cooled in
the form of individually wrapped slices.
The reduced fat Pasteurized Process American Cheese Product was analyzed to
have the following composition:
TABLE 1
______________________________________
Moisture 57.43%
Fat 8.46%
Protein 20.80%
Lactose 5.30%
Salt 2.33%
pH 5.58%
______________________________________
In addition to the analytical results, flavor, texture and standard melt
test evaluations were conducted on the reduced fat cheese product.
The product was determined to have a mild American cheese flavor and an
oxidized fat type off flavor, a somewhat sticky texture and a 21.4%
increase in area after melting corresponding to a "fair" melt
characteristic.
EXAMPLE 9
Viscous Dressing Product
A reduced calorie, reduced fat viscous dressing product was prepared
utilizing the microfragmented anisotropic xanthan/protein complex
dispersion of Example 3, lot 2, containing the hydrated xanthan/protein
complex microfragments in aqueous dispersion, and having a solids content
of 16.0 weight percent, based on the total weight of the dispersion. In
preparing the new dressing product, the following ingredients were
utilized:
______________________________________
Weight
Ingredient Percent
______________________________________
Water 15.70
Soybean Oil 40.35
microfragmented anisotropic xanthan/protein
30.00
dispersion of Example 3
Eggs 10.20
Vinegar 2.67
Spice Blend 1.08
______________________________________
In preparing the dressing, the water, eggs and spice blend were thoroughly
mixed in a Hobart mixer (Model A200D with a "D" wire whip). After mixing
these ingredients, the oil component was slowly added to the blend under
maximum agitation conditions in the Hobart mixer to form a dressing
preemulsion. The vinegar component was subsequently blended into the
preemulsion to form an acidified preemulsion. The microfragmented
anisotropic xanthan/protein complex dispersion of Example 3 was then added
to the acidified preemulsion, and the resulting mixture was blended in the
Hobart mixer at medium mixing speed, to produce a smooth, homogeneous
dressing premix. The premix was homogenized by passing it through a
conventional colloid mill [Charlotte Model SD-2, Continuous Mayonnaise
Machine with 3 HP motor. Supplied by Chemicolloid Laboratories Inc.,
Garden City Park, N.Y.] with a temperature rise of 10.degree. F. to form
viscous mayonnaise-type product having approximately half the fat content
of a conventional mayonnaise. The product had a calorie content of 53
calories per 14 gram serving, as compared with a calorie content of 100
calories per 14 gram serving for a conventional mayonnaise. The reduced
calorie product had a smooth and creamy mouthfeel, and was even more
viscous and had a heavier body than a conventional mayonnaise product.
Mayonnaise-type products containing a microfragmented anisotropic
xanthan/protein complex dispersion having reduced viscosity and body may
be readily prepared by utilizing a microfragmented xanthan/protein complex
dispersion starting ingredient having a lower solids content in preparing
the viscous dressing product.
EXAMPLE 10
Reduced Fat Viscous Dressing Product
A reduced fat viscous dressing product like that of Example 9, but having
even lower oil content, was prepared utilizing the microfragmented
anisotropic xanthan/protein complex dispersion of Example 3, lot 2, having
a solids content of 16.0 weight percent. In preparing the reduced calorie
salad dressing product, the following components were utilized:
______________________________________
Ingredient Percent
______________________________________
Water 9.14
Soybean Oil 16.62
microfragmented anisotropic xanthan/protein
11.10
dispersion
Eggs 5.18
Starch Paste 54.08
Salt & Spice Blend 3.86
Gums 0.02
______________________________________
The starch paste is prepared from food grade starch (e.g., corn or
tapioca), together with sugar, vinegar and spices. The starch is formed
into paste by heating with sufficient water to gelatinization temperature,
to fully gelatinize the starch component, and to provide a fully
gelatinized paste having a starch content of 8.2 weight percent.
In preparing the dressing, the water, eggs, salt and spice blend were mixed
in a Hobart blender. After mixing these ingredients, the oil component was
slowly added to the blend under maximum agitation conditions to form a
dressing preemulsion. The vinegar component was subsequently blended into
the preemulsion to form an acidified preemulsion. The microfragmented
dispersion of Example 3 was then added to the acidified preemulsion, and
the resulting mixture was blended in the Hobart mixer at medium mixing
speed, to produce a smooth, homogeneous dressing premix. The premix was
homogenized by passing it through a conventional colloid mill [Charlotte
Model SD-2 Continuous Mayonnaise Machine with 3 HP motor], with a heat
rise of 10.degree. F. to form an emulsion. The mayonnaise style low fat
dressing product was formed by combining together in a Hobart Mixer, the
emulsion and the amount of starch paste in the formulation and blending at
the lowest speed until the components were homogeneously mixed. The
viscous mayonnaise-style product had a vegetable oil content of about 17.5
weight percent, which is a significantly lower fat content than a
conventional mayonnaise. The product had a calorie content of 30 calories
per 14 gram serving, as compared with a calorie content of 100 calories
per 14 gram serving for a conventional mayonnaise. The product had a
smooth texture, similar to conventional reduced calorie salad dressings.
EXAMPLE 1
A 17.5 weight percent fat mayonnaise type product was produced utilizing
microfragmented xanthan/protein complex dispersions as a bodying agent
contributing a creamy mouthfeel to the products.
17.5% Fat Mayonnaise Type Product
In preparing the 17.5% low fat mayonnaise-type products, a starch/oil
slurry, and a water/spice blend were first prepared. The starch/oil slurry
was prepared from the following ingredients:
______________________________________
Starch/Oil Slurry
Weight
Ingredients Percent
______________________________________
Canola oil 77.53
Pregelatinized corn starch
22.29
Xanthan Gum 0.18
______________________________________
The oil was metered into a 4000 gallon slurry tank, and under high
agitation provided by a propeller type mixer, were added in succession,
the xanthan gum (preslurried in a small amount of oil) and the starch. A
small amount of beta carotene was added as a coloring agent.
The water/spice blend was prepared from the following ingredients:
______________________________________
Water/Spice Blend
Ingredients Percent
______________________________________
Water 66.23
Corn Syrup Solids 18.30
Egg Yolk 6.32
Vinegar 5.93
Sucrose 3.16
Salt 1.44
Microcrystalline cellulose
1.26
Spices & Flavors 0.62
Whey Protein Concentrate
0.28
Potassium sorbate 0.25
Sodium caseinate 0.06
Xanthan gum 0.05
______________________________________
The water/spice blend was prepared in a separate tank by first introducing
approximately two-thirds of the formula water to the tank. The
microcyrstalline cellulose was subsequently added and dispersed with a
propeller type mixer at high speed. The xanthan (slurried in a small
amount of oil), and the whey protein concentrate, with a small portion of
the corn syrup solids were added and blended well. The well mixed contents
of the water/spice tank were recirculated through a Silverson homogenizer
mixer.
In this regard, as shown in FIG. 2, the manufacturing apparatus comprises a
product mixing and holding tank 202, a tank outlet conduit 204 and the
Silverson in-line continuous mixer-homogenizer 206 which itself comprises
a stator chamber 208, and a high shear rotor 210 powered by motor 212. The
discharge from the stator head may be returned to the tank 202 or
discharged to emulsifier 214 by means of conduits 216, 218, respectively
under operator control. A pump 220 controls the flow rate through the
Silverson homogenizer 206. The in-line continuous flow mixer homogenizer
206 (Model 425L of Silverson Machines, Ltd., Waterside, Chesham, England)
was particularly designed for continuous operation at high speeds, and
incorporated a high-shear slotted rotor/stator processing workhead 208,
210. The action of the high shear workhead caused materials inside the
head to be subjected to intense hydraulic shear by the high speed rotation
of the rotor 210 inside the confined space of the stator chamber 208. In
this regard, centrifugal force generated by the rotor drives the contents
of the head towards the periphery of the head where solid and liquid
ingredients were milled in the fine precision clearance between the rotor
blade ends and the inner stator wall. Further centrifugal force expels
materials from the head, imparting mechanical shear between the rotor tips
and the edges of the stator perforations. Finally, also under the
influence and control of the pump 204, the contents of the head are driven
by the same centrifugal force through the machine outlet and along the
pipeline 216, 218; at the same time fresh materials are drawn in at the
inlet to keep the head continuously charged.
In order to achieve a higher degree of homogenization or comminution than
obtained by a single passage, the product was passed several times through
the machine by a process of recirculation.
The Silverson mixer had a slotted head and an energy input of 10 HP. The
water/spice blend was circulated for about 3 minutes until there were no
visible lumps in the mixture. The vinegar was subsequently added to the
blend in the tank to acidify the xanthan/protein solution to initiate
fiber formation while maintaining recirculation of the mixture through the
Silverson homogenizer to provide a microfragmented anisotropic dispersion.
The acidified, water/spice blend containing the microfragmented dispersion
was recirculated through the Silverson mixer, operated as described above,
for about 2 minutes. A sample of the microfragmented anisotropic
xanthan/protein complex dispersion was taken prior to addition of the
remaining ingredients. The remaining third of the formula water was then
added, together with the remaining ingredients of the water/spice blend,
while recirculation continued through the Silverson mixer for about 3
minutes.
The dressing product emulsion was then prepared by combining the oil/starch
slurry and the water/spice blend in the proportions of 20.64% oil starch
slurry and 79.36% water/spice mixture. In this regard, the contents of the
oil/slurry tank were pumped into the water/spice tank under agitation
provided by the propeller-type mixer provided in the tank. Agitation was
continued for about 3 minutes until a homogeneous blend was produced. The
contents of the tank were then pumped in a single pass through the
Silverson homogenizer into a feed tank for a continuous, inline
homogenizer for salad dressing emulsion preparation and processed by the
homogenizer.
The resulting microfragmented anisotropic xanthan/protein complex
containing mayonnaise-like product oil was filled into one liter glass
jars. The product was evaluated organoleptically and found to have a
creamy mouthfeel and viscous texture provided at least in part by the
microfragmented xanthan/protein dispersion. The product had a calorie
content of 35 calories per 14 gram serving, as compared with a calorie
content of 100 calories per 14 gram serving for a conventional mayonnaise.
Rheological properties of the product were determined by using a Haake VT24
Viscotester, to be as follows:
______________________________________
Viscosity Data
17.5% Fat Mayonnaise Style Product
Haake Haake
Time Yield Value
Viscosity
______________________________________
24 hours 2200 750
2 weeks 2550 800
______________________________________
The sample of the microfragmented anisotropic xanthan/protein complex
dispersion was subsequently stored at room temperature for about 10
months. After the 10 month storage period, the microfragmented anisotropic
xanthan/protein complex dispersion appeared to be free of microbial
growth. A sample of the dispersion was then evaluated by scanning electron
microscopy and found to predominantly comprise microfragments having a
major dimension of less than about 10 microns.
A sample of the finished mayonnaise product was also retained at room
temperature for about 10 months. The product was found to maintain its
phase stability without phase separation.
EXAMPLE 12
A reduced calorie, reduced-fat viscous dressing product was prepared having
an extremely low vegetable oil content of approximately 5 weight percent,
utilizing an aqueous dispersion of finely ground, fibrous particles of a
xanthan/protein complex. The utilization of the xanthan/protein complex in
the dressing formulation improved the textural, visual and mouthfeel
characteristics of the significantly reduced fat viscous product. The
aqueous, anisotropic xanthan/protein complex dispersion was prepared from
the following materials:
______________________________________
Ingredient Amount
______________________________________
Water 1,478.00 Grams
Xanthan Gum 3.65 Grams
Whey Protein Concen. 21.95 Grams
Vinegar 129.88 Grams
______________________________________
The xanthan and whey protein concentrate were dispersed in the water in a
laboratory beaker and then sheared under microfragmentation conditions by
means of a Brinkmann Kinematica homogenizer (Model #PTA35/2G of Brinkmann
Instruments Co., Division of Sybron Corporation, Westbury, N.Y.) placed in
the beaker, running at the mid-range speed, which is approximately 15,000
rpm. Vinegar was added and a milky, opaque suspension of finely comminuted
fibers was produced. This resultant aqueous dispersion was utilized as a
bodying agent which contributed a creamy mouthfeel in the following
formulation.
______________________________________
Ingredient Percent
______________________________________
Emulsion 20%
Water 50.50
Hydrogenated Oil 22.50
Emulsifiers 2.00
Whole egg mix 25.00
Base 80%
Water 38.62
Xanthan/Protein 25.00
Complex dispersion
Corn Syrup Solids 10.00
Vinegar 7.62
Instant Starch 9.50
Sugar 8.00
Spice Mix 1.26
______________________________________
In preparing the dressing, the emulsion portion is obtained by combining in
a Hobart Mixer, the water, whole egg mix, emulsifiers and salt, and mixing
to properly dissolve and disperse the ingredients. After mixing these
ingredients, the oil component was slowly added to the blend under maximum
agitation conditions to form an emulsion.
The starch paste portion of the formula containing the microfragmented
dispersion of the xanthan/protein complex was prepared by first dry
blending the corn syrup solids, sugar, pregelatinized starch and spice
mix. In the mixing bowl of a separate Hobart Mixer, the water, vinegar and
the microfragmented dispersion are combined. The dry mix with the
pregelatinized starch is added under vigorous agitation. When the starch
has fully hydrated to a smooth paste, the emulsion is blended in. In the
final stage of preparation, the emulsion/starch blend is passed through a
colloid mill (Charlotte Model SD-2) with a 6.degree. F. heat rise to form
the low fat viscous dressing product.
The resulting product had the appearance and mouthfeel of a viscous
dressing with higher levels of fat than the 5 weight percent it contained.
EXAMPLE 13
Dairy Based Viscous Dips
A shelf-stable, non-refrigerated, reduced fat dairy based viscous dip
product was prepared utilizing a xanthan/protein gel as a bodying agent
contributing fat-like organoleptic properties in the dip formulation. A
full-fat control was also prepared for comparison purposes. In preparing
each of the full-fat control and the reduced-fat product, a mayonnaise
portion and a sour cream base portion were prepared separately, which were
subsequently blended to form the dip product. The mayonnaise portion of
both the control and the reduced fat dairy based viscous dip product was
prepared from the following ingredients:
______________________________________
Ingredient Weight Percent
______________________________________
Water 5.32
Soybean Oil 83.90
Eggs 8.10
Spice Blend 2.68
______________________________________
The formula water, eggs and spice blend were mixed, and the oil was added
under high agitation conditions to form preemulsion. The preemulsion was
passed through a Charlotte Model SD-2 colloid mill with a 10% heat rise to
form an emulsion.
Separately, sour cream base portions for the full fat control product, and
for a forty percent fat replacement xanthan/protein ("X/P") gel containing
reduced fat product, were respectively prepared from the following
ingredients:
______________________________________
Ingredients Control X/P Gel Product
______________________________________
Water 27.41 31.00
Sour Cream 50.00 31.00
Herb/Spice Blend 19.03 19.03
Xanthan/Protein Gel
0.0 15.50
Lactic Acid (88%)
1.90 1.90
Phosphoric Acid (80%)
0.22 0.22
Soybean Oil 0.95 0.95
Sorbic Acid 0.24 0.24
Gums 0.25 0.25
______________________________________
The xanthan/protein gel component was prepared from the following
materials:
______________________________________
Ingredient Amount
______________________________________
Water 2 Liters
Xanthan Gum 26.67 Grams
Dried Egg Whites 13.34 Grams
Lactic Acid (50%) 20 Milliliters
______________________________________
In preparing the gel, the xanthan and egg whites were thoroughly dispersed
in the formula water. The lactic acid was subsequently added to the
mixture with very gentle agitation. Gelation was substantially completed
upon standing several minutes, to provide the xanthan/protein gel product.
To prepare the sour cream base portion, the gums were slurried in oil and
the slurry was added to the formula water. The remaining ingredients were
added and dispersed in the resulting blend. Both the control sour cream
base portion and xanthan/protein gel sour cream base were each separately
combined with the mayonnaise portion prepared as previously described at a
weight ratio of 42:58 in a Hobart blender at low speed. The
xanthan/protein gel product was evaluated organoleptically, and compared
with the full fat control sample.
The dairy based dip containing the xanthan/protein gel exhibited
surprisingly similar characteristics to the dip that contained 40% more
sour cream.
The gum/protein gel complex was found to have an exceptional ability of
imparting thick and creamy characteristics to food products such as
dressing and dip formulations when used as a partial replacement for a
full fat product. In particular, the addition of a gum/protein gel complex
to the basic formulation of a dairy/mayonnaise dip allowed for the
replacement of 40% of the full fat sour cream with no reduction in product
attributes including flavor, texture, mouthfeel and appearance.
EXAMPLE 14
Barbecue Sauce
A reduced calorie barbecue sauce having exceptional "cling" properties was
prepared, by blending a barbecue sauce base portion and a microfragmented
xanthan/protein complex dispersion at a 9:1 weight ratio. The barbecue
sauce base portion was prepared by blending and cooking the sauce base
blend to a starch gelatinization temperature of 190.degree. F. to fully
gelatinize the starch, and subsequently cooling the gelatinized blend to
room temperature to provide a sauce base having the following composition:
______________________________________
Barbecue Sauce Base
Ingredient Percent
______________________________________
Water 16.5
Corn Syrup 30.00
Vinegar 24.00
Tomato Puree 20.00
Spices 6.00
Starch 2.00
Soybean Oil 1.40
Gum 0.10
______________________________________
A microfragmented anisotropic xanthan/protein dispersion was prepared
according to the following formulations:
______________________________________
Ingredient
______________________________________
Amount
Water 2.80 Liters
Xanthan Gum 8.33 Grams
Dried Egg White 50.00 Grams
Vinegar - 120 Grain 245.00 Grams
Barbecue Sauce
Percent
Barbecue Sauce Base 90.0
Xanthan/Protein 10.0
Complex Dispersion
______________________________________
The xanthan and dried egg whites were dispersed in the formula water in a
laboratory beaker. A Brinkmann Kinematica homogenizer (Model #PT10/35
utilizing a PTA 352G generator head) was inserted into the fiber forming
solution in the beaker. The Brinkmann Homogenizer is an instrument
combining cavitation and mechanical shearing action for homogenization,
dispersion and emulsification of solids or liquids. The destructive action
of the Brinkmann Homogenizer is based on two interrelated forces: direct
mechanical action and cavitation, which is the formation of partial
vacuums in a liquid by a swiftly moving solid body and the resulting
breakdown of substances in that liquid when those vacuums cease to exist.
In the Brinkmann Homogenizer, a generator head, rotating at ultra high
speed, creates a cutting, ripping and demolishing action. At very high
rotational speed, vacuums are created in the chambers between the teeth of
the generator and the blades rotating behind them, shearing
xanthan/protein complex fragments into microfragments of irregular shape.
The Brinkmann Homogenizer consists of two principal components: a) the
basic assembly, consisting of high-speed 700W motor, PCU speed control,
stand and mounting hardware and b) the generator. Selection of the
appropriate basic assembly is dependent on the generators to be used,
which in turn depends on the materials and volumes to be homogenized. The
35/2 designation relates to the number of rotating and stationery rings on
the homogenization end of the generator head, with the /2 designating
rotors (one outer ring, one inner ring) being best for homogenization.
Vinegar was added and a milky opaque suspension of comminuted fibers was
produced. The barbecue sauce base was blended with the xanthan/protein
complex microfragment dispersion in a 9:1 weight ratio until well
dispersed by means of a Hobart Blender. The blended product was evaluated
and found to have improved body, texture and cling characteristics. In
particular, it was shown that the addition of the microfragmented
comminuted xanthan/protein complex dispersion to a barbecue sauce resulted
in a product with superior coating capacity on barbecued chicken, with
greater moisture retention in the cooked meat when compared with control.
EXAMPLE 15
Frozen Dessert Product
A reduced calorie, reduced fat frozen dessert product was prepared
utilizing the microfragmented anisotropic xanthan/protein complex
dispersion of Example 3, Lot 2 containing the hydrated xanthan/protein
complex microfragments in aqueous dispersion, and having a solids content
of 15 weight percent, based on the total weight of the dispersion. In
preparing the new frozen dessert product, the following ingredients were
utilized:
______________________________________
Weight Amount
Ingredients Percent (kg)
______________________________________
Water 28.66 2.600
Condensed skim (33.35% T.S.)
37.48 3.400
corn syrup 36 DE 9.38 0.851
sucrose solids 10.75 0.975
stabilizer blend of locust
0.20 0.018
bean gum, guar gum,
dextrose, whey solids,
calcium carrageenan
emulsifier blend of mono &
0.20 0.018
diglycerides
microfragmented 13.33 1.209
anisotropic
xanthan/protein dispersion
of Example 3
______________________________________
In preparing the frozen dessert mix, the condensed skim, corn syrup,
sucrose, stabilizer, emulsifier and 80% of the water were thoroughly mixed
in a Lanco (Kansas City, Mo.) high speed mixer. After mixing, these
ingredients were passed through a HTST (Crepaco, Cedar Rapids, Iowa) and
homogenizer (Manton-Gaulin, Everett, Mass.) system. At a flow rate of 0.28
cubic meters per hour, the base mix was preheated to 65.5.degree. C. and
then homogenized at dual stage pressure of 140 kg/cm.sup.2 and 35
kg/cm.sup.2, respectively. In addition, the temperature of the base mix
was raised to 82.2.degree. C. and held for 32 seconds. Prior to release
from the HTST, the mix was cooled to less than 7.degree. C. The base mix
was then stored or aged at 4.4.degree. C. for 24 hours.
Before the freezing process, the microfragmented anisotropic
xanthan/protein complex dispersion of Example 3 was blended in a Waring
table-top blender with the remaining water. The resultant mixture,
previously made base mix, and artificial vanilla (at 0.07%) were combined
and then cold homogenized using a single-piston homogenizer with a
single-stage pressure of 140 kg/cm.sup.2. The 9.07 kg of final mix was
frozen to a finished weight of 613 g/liter using an 18.9 liter batch
freezer (Model 20 of Emery Thompson, Bronx, N.Y.). Immediately after
freezing, the product was transferred to the -28.9.degree. C. hardening
room.
The vanilla frozen dessert product contained 0% milkfat and had 20% less
calories than a conventional ice milk. The fat substituted dessert had a
calorie content of 20 calories per 100 gram serving, as compared to a
calorie content of 150 calories per 100 gram serving for a conventional 4%
milkfat ice milk. The reduced fat and calorie product had a similar body
and texture as compared to a conventional ice milk, with increased
firmness. There was perceived fatty mouthfeel as measured against a 0%
milkfat frozen dessert and the conventional ice milk.
EXAMPLE 16
A fibrous complex of highly substituted, high molecular weight
carboxymethyl cellulose complexed with a mixture of egg albumen and whey
protein was prepared for subsequent utilization in food products.
In preparing the fibers, 8.4 grams of food grade carboxymethyl cellulose
("CMC") having an average degree of substitution of about 0.9, a viscosity
of about 3500 centipoise as measured on a Brookfield LVF viscometer, using
Spindle #4 at 1 weight percent carboxymethyl cellulose dissolved in water
at 30 rpm and 25.degree. C., and an average molecular weight of about
150,000 daltons approximated using intrinsic viscosity (9H4F carboxymethyl
cellulose product of Hercules, Inc., Wilmington, Del.) was suspended in
2,800 milliliters of distilled water, and the suspension was heated to
about 130.degree. F. to provide a fully dissolved carboxymethyl cellulose
solution. The carboxymethyl cellulose solution was then chilled in a
refrigerator for several hours (about 4 hours) to a temperature of
22.degree. C. To the carboxymethyl cellulose solution was added 33.6 grams
whey protein concentrate ("WPC"), Kraft Whey Protein Concentrate
containing about 35% by weight protein, followed by 33.6 grams of dried
egg white ("DEW"), Kraft Blue Label #207 Dried Egg White, while the
carboxymethyl cellulose solution was stirred in a Waring blender at medium
speed (about 1025 rpm). The resulting complex fiber-forming solution
mixture was stirred in the Waring blender for 5 minutes and then acidified
in a 4 liter beaker with 1 molar hydrochloric acid with stirring using a 1
cm wide 9 inch long spatula to produce long, stringy fibers. Fibers
started to form when the solution was acidified to pH 6.0. These fibers
were very white and similar to the xanthan gum/protein complex fibers
prepared under similar conditions.
The fibers were analyzed and found to have the following composition:
______________________________________
Composition of Edible CMC/Protein Complex Fibers
Component Weight Percent
______________________________________
Protein 10.90
Carbohydrate 2.90
Fat 0.60
Ash 0.14
Moisture 84.50
______________________________________
The carboxymethyl cellulose/protein complexed fibers were white, bland,
chewy and had meat-like or seafood-like texture. One part of these
carboxymethyl cellulose/protein complex fibers was boiled in 10 parts of
water for 3-5 minutes to give firm, stable, chewy, white and bland fibers,
which could be flavored with meat, poultry, fish, shellfish, or other
seafood flavors to give carboxymethyl cellulose/protein based meat,
poultry, fish, shellfish and other seafood products, as previously
described with respect to xanthan gum/protein fiber utilization and food
product formulation.
Chicken flavored patties were prepared having a meaty, chewy texture and
excellent flavor. The above procedure was also carried out with other
carboxymethyl cellulose products of Hercules, Inc., having different
degrees of substitution, and molecular weight as follows:
______________________________________
Carboxymethyl Degree of
Cellulose Viscosity Carboxymethyl Product
Molecular Wt
Centipoise
Substitution Designation
______________________________________
150,000 500-2000 0.4 4H1F
150,000 1500-3000 0.7 7HF
70,000 70,000 1.2 12M31F
______________________________________
The viscosity was measured as previously described for the 9H4F
carboxymethyl cellulose, except that a Spindle #3 was used in the
Brookfield LVF viscometer. The molecular weight was estimated based on
intrinsic viscosity data.
None of these products formed fibers with the egg white and whey protein
concentrate when following the same procedure which produced fibers using
the 9H4F product having a degree of substitution of 0.9 and an average or
molecular weight of about 150,000 daltons.
EXAMPLE 17
In order to prepare highly substituted carboxymethyl cellulose fibers for
high shear fragmentation, 9 g. of carboxymethyl cellulose (9H4F
carboxymethyl cellulose from Hercules, Inc.) were dispersed in 3000
distilled water and the dispersion was stirred in a Waring Blender at
medium speed at 22.degree. C. for 5 minutes. 36 g. WPC (Kraft whey protein
concentrate, containing 35% protein) into the carboxymethyl cellulose
solution in the Waring blender with stirring under the same conditions. To
this mixture was added 36 g. KDEW (Kraft dried egg whites, blue label) in
the Waring blender with stirring under the same conditions, followed by
stirring in the Waring blender under the same conditions for 5 minutes.
To the resulting fiber forming solution was added 79 ml. of 1 m HCl which
was allowed to diffuse throughout the mixture (with punching holes in the
reaction mixture using a 1 cm.times.20 cm spatula). The acidified
carboxymethyl cellulose/protein mixture was stirred by spatula to generate
fibers. This procedure was repeated five times and the carboxymethyl
cellulose/protein fiber suspensions were combined.
The fibers were collected and stored in a 5.degree. C. refrigerator before
boiling. The previous steps were repeated three times, and the resulting
fibers were combined to produce 3 gallons of carboxymethyl cellulose/egg
white/whey protein complex which was then boiled for 5 minutes to
stabilize the fibers, washed and drain-dried, boiled for 5 minutes, washed
with cold tap water and drained. The boiled, washed fibers were mixed with
water to produce a slurry, and then subjected to intense shear through the
use of a CD150 cell disruptor generally as described in Example 1 to break
the carboxymethyl cellulose/protein fibers up into small microfragments
(12,000 to 15,000 psi, 90.degree.-130.degree. F.) to produce a fluidized
aqueous dispersion having a white, smooth, creamy texture, and a bland
taste. The dispersion was centrifuged at 1000 g, 10.degree. C. for 10
minutes to provide a creamy concentrated dispersion having a solids
content of 25.6 weight percent.
EXAMPLE I8
A carboxymethyl cellulose/protein complex was prepared on a pilot plant
scale apparatus like that of FIG. 1 by suspending 280 grams (0.396 lb.) of
carboxymethyl cellulose (Hercules 9H4F) in 132 pounds deionized water, and
blending the suspension with a Triblender batch mixer at 22.degree. C. for
5 minutes. To the supsension-solution was added 720 grams (1.58 lb.) whey
protein concentrate (Kraft WPC), followed by 720 grams dried egg whites
(Kraft Blue Label), to the solution, and the gum/protein mixture was
blended under these conditions for 5 minutes. As generally shown in FIG.
1, the carboxymethyl cellulose/protein solution was pumped by a pump 110
while hydrochloric acid 114 (2.5 Normal) was metered into the
carboxymethyl cellulose/protein mixture line and the acidified mixture
conducted through the hold tube 113 and the pump 118, at a rate such that
the fiber suspension coming out of the fiber pump 118 was at about pH 3.0.
The fibers are long, stringy, and highly anisotropic [FIG. 22].
The fibers produced in this manner were drained on screens. This procedure
was repeated to produce multiple batches of fibers. The drained fibers
were boiled in water for 6 minutes and drained again on screens. Similar
fibers were successfully prepared in the same manner using the
carboxymethyl cellulose with egg white and sodium caseinate in a 1:4:4
weight ratio.
Fibers of carboxymethyl cellulose/egg white +whey protein complex or
carboxymethyl cellulose/egg white/caseinate complex were chopped into
small pieces using a Pentax homogenizer and then microfragmented at a 5
weight percent totals solids level by conducting 8 passes through a CD 150
cell disruptor (A.P.Z. Gaulin Corp., Boston, Mass.) at 15,000 psi and a
130.degree. F. discharge temperature. The microfragmented aqueous
dispersion was concentrated by passage through a Turbafilm evaporator as
described hereinabove, to provide a thick, viscous microfragmented aqueous
dispersion having a total solids content of 17 weight percent. The
resulting dispersion was very white, bland, smooth and creamy.
The microfragmented carboxymethyl cellulose/ protein complex dispersion is
very white, smooth, creamy and bland and can be used as a fat substitute
in a wide variety of food products. The fluidized carboxymethyl
cellulose/protein complex solids may be collected by centrifugation at
4,100.times.g. and at 10.degree. C. for 10 minutes The centrifuged pellets
of the fluidized carboxymethyl cellulose/protein complex are very white,
smooth, creamy and can be used as a fat substitute.
The dimensions of the carboxymethyl cellulose/protein complex and
xanthan/protein complex microfragments and the emulsion-droplet sizes of
model emulsions were measured by using a Leeds and Northrup Microtrac
particle size analyzer.
The various aqueous microfragmented polysaccharide/protein complex
dispersions which may be prepared from different combinations of protein
and polysaccharide components have microstructural and rheological and
other property differences which provide corresponding performance
differences in food product utilization.
Although it has various colloidal, microstructural, rheological and other
differences from the microfragmented xanthan/egg white/whey protein
complex as previously described, the microfragmented carboxymethyl
cellulose/egg white/whey protein complex is smooth, creamy, has a fat-like
mouthfeel and can be used as a fat replacer.
EXAMPLE 18A
A mayonnaise model emulsion was prepared by the formula and procedure as
described below:
Formula: soybean oil, 39.6%; the concentrated CMC/protein dispersion of
Example 17 (25.6% solids), 39.6%; whole egg mix, 8.8%; Marshall yolks,
1.8%; sugar, 0.75%; salt, 0.25%; deionized water, 3.2%; and 6% vinegar,
6%.
Procedure
1. Dissolve 2.5 gram salt and 7.5 gram sugar in 32 grams of deionized water
in a one-gallon Hobart blender.
2. Disperse 88 grams whole egg mix, 18 gram Marshall yolks, and 39.6 grams
of the concentrated 25.6 weight percent aqueous carboxymethyl
cellulose/protein complex dispersion in the salt/sugar solution.
3. Add soybean oil in small portions (i.e., 60 ml at a time) into the
dispersion while blending in the Hobart blender at the highest speed
(i.e., speed 3) and at 22 C.
4. Change the mixing speed from fast to medium (i.e., from Speed 3 to 2)
after half the soybean oil is added and then add the rest of the oil in
small portions into (3) while blending at the medium speed.
5. Add 60 ml of 6% vinegar in small portions (i.e., 10 ml at a time) into
(4) while blending at the medium speed.
6. Continue blending (5) at the medium speed for 1 minute after everything
is added to form a mayonnaise pre-emulsion.
7. Homogenize the mayonnaise pre-emulsion on a Gaulin bench top colloid
mill at 22.degree. C. to form a mayonnaise model emulsion.
The viscosity of mayonnaise model emulsions was measured on a Haake VT24
viscotester using a No. 4 spindle blade at 22.degree. C.
The mayonnaise-type product prepared with the carboxymethyl cellulose/whey
protein+egg white microfragmented aqueous dispersions had smaller emulsion
droplets than a control mayonnaise-type product prepared with a
xanthan/whey protein+egg white microfragmented dispersion, indicating
potentially higher stability for the carboxymethyl cellulose/protein
complex product. The viscosity of carboxymethyl cellulose/protein based
mayonnaise is very similar to a conventional mayonnaise control while the
viscosity of the xanthan/protein complex based mayonnaise type control is
slightly too thick, which may be due to the fact that the xanthan/protein
complex is less dense and adsorbs more water than the carboxymethyl
cellulose/protein product as discussed in Example 18C. The xanthan/protein
complex dispersion based mayonnaise type product was perceived only
slightly creamier than the carboxymethyl cellulose/protein complex based
mayonnaise type product.
The particle size of the precipitated complex was determined by adding a
small amount of fibers thoroughly dispersed in a pH 5.5. citrate phosphate
buffer solution.
A few drops of the dispersion were added to the distilled water circulating
in the Microtrac analyzer. Size measurement results from an average of 3
runs were as follows:
______________________________________
Mayonnaise Model Emulsions Prepared With
Microfragmented Polysaccharide/Protein Complexes
Dispersion Particle
Size-Largest Dimension
Viscosity
Polysaccharide
(microns) (HU)*
______________________________________
CMC (carboxymethyl
3.89 780
cellulose)
______________________________________
*HU = Haake unit
EXAMPLE 18B
A vanilla frozen dessert product was prepared utilizing the carboxymethyl
cellulose/egg white+whey protein complex dispersion of Example 18 as
described in Example 15, and comparison vanilla frozen desserts were
prepared using a full fat control and a xanthan/egg white+whey protein
complex dispersion.
The vanilla frozen dessert utilizing the carboxymethyl cellulose/protein
complex dispersion was perceived as creamier than both the full fat
control and the xanthan/protein based products. This may be due to the
fact that the carboxymethyl cellulose/protein complex at the pH of the
frozen dessert is very negatively charged and well dispersed. It is noted
that the viscosity of the carboxymethyl cellulose/protein complex
increases more sharply (especially at high concentration) than viscosity
of the xanthan/protein dispersion as the pH increases.
EXAMPLE 18C
The aqueous, microfragmented carboxymethyl cellulose/protein complex
dispersion of Example 18 was characterized by various microscopic methods.
The concentrated sample of carboxymethyl cellulose/protein complex from
Example 18 was diluted in 0.05M sodium cacodylate buffer (pH 5.5) and
vortexed in order to disperse the fragments. The diluted sample was placed
on a glass slide, coverslipped and observed using differential
interference contrast optics on a Zeiss Axiophot photomicroscope.
Concentrated samples were diluted using 0.05M sodium cacodylate buffer (pH
5.5), based on optical opacity. Due to the small size of the material a
special method was ed for carrying the particles through the various
processing steps. Polycarbonate membranes (Nuclepore) with pore diameters
of 0.1 microns were used to make a sandwich between which the diluted
carboxymethyl cellulose/protein complex was placed to allow free flow of
fixatives, dehydrating agents, and other processing agents while retaining
the material in a diluted form suitable for scanning electron microscope
("SEM") observation. The material was fixed in 2% glutaraldehyde in 0.05M
sodium cacodylate for 15 minutes, dehydrated in an acetone-water series to
100% acetone and critical point dried using carbon dioxide. The sandwich
was subsequently dismantled and one of the two membranes with attached
particles was affixed to an SEM stub and gold coated.
The 25% solids carboxymethyl cellulose protein complex was encapsulated in
4% agar and immediately fixed in 2% glutaraldehyde in 0.05M sodium
cacodylate buffer for overnight storage at 4.degree. C., rinsed twice in
the same buffer, post-fixed in 1% osmium tetroxide in the same buffer for
1 hour at 4.degree. C. followed by 30 minutes at room temperature. After a
buffer rinse, the material was dehydrated in a graded ethanol series
followed by two rinses in 100% acetone, 10 minutes each and embedded in
Epon/Araldite epoxy resin. Thin sections were stained in 2% aqueous lead
citrate and uranyl acetate. Observation and recording of images was
performed using a Zeiss C-10 transmission electron microscope.
EXAMPLE 18D
After microfragmentation by microfluidization, the carboxymethyl
cellulose/protein complex is broken into fragments which range in size
from approximately 0.2 to 5 microns. These particles are neither spherical
or filamentous in shape as determined by LM (FIG. 24), SEM (FIG. 25) or
TEM (FIG. 26). Based on all three methods, it can be said that the
material after microfluidization appears as irregular fragments of a wide
size range.
When viewed by SEM, as shown in FIG. 25, the fragments appear as irregular
shapes which vary in density or degree of openness. While some fragments
are relatively dense or closed, the majority are best described as
sponge-like. Numerous openings occur on the surface and extend into and
even through the fragments. This is supported by the TEM images shown in
FIG. 26, which present sectional profiles through the material. The
profiles of most fragments emphasize the open nature of this material.
The aqueous carboxymethyl cellulose/whey protein/egg white complex of
Example 17 having a total solids content of about 25.8% by weight as
determined by microwave moisture analysis, was subjected to a variety of
physical measurements. Samples for viscosity measurements were prepared at
various levels of concentration, pH and added sodium chloride. Suspensions
of the material were prepared by weighing out the concentrated material
into scintillation vials, adding NaCl if necessary, and diluting to the
desired concentration by addition of distilled water or buffer.
Citrate/phosphate buffers with pH ranging from 3.0 to 7.0 were used to
adjust the pH of the suspensions. The pH range was extended by adding 6M
NaOH or 6M HCl to the vials taking care not to mix the concentrated base
and the complex before shaking. The samples were shaken vigorously by hand
and then homogenized with a Polytron homogenizer for about 30 seconds. The
pH of each sample was measured prior to the viscosity measurements. The
composition of samples measured in this study are listed below.
______________________________________
The Composition of Microfragmented
Carboxymethyl Cellulose/Protein Complex
Component
Percent
______________________________________
Moisture 74.41
Fat 0.55
Protein* 19.1
Carbohydrate
2.4
Ash 0.09
______________________________________
*The protein consists of 33% ovalbumin, 25% betalactoglobulin, and 14%
alphalactalbumin among which 54% ovalbumin and 18% betalactoglobulin are
crosslinked
Flow curves of the samples (FIGS. 39a, 39b, and 39c) were measured using a
Carri-Med Controlled Stress Rheometer at 25.0 (.+-.0.1) degrees C.
Measurements were made using a cone and plate geometry with either a 6 cm
1 degree 1'30" cone or a 4 cm 1 degree cone. The instrument was operated
in the controlled shear rate mode. Shear rates were varied from 0 to 150
s.sup.-1 over a three minute period (up curve), then held at 150 s.sup.-1
for 1 minute (peak hold) and then lowered back to 0 s.sup.-1 over another
three minutes (down curve). This experimental procedure was utilized to
subject all of the samples to the same flow history, and to minimize any
time dependent shear effects. For comparison purposes, the viscosity at a
shear rate of 50 s.sup.-1 from the down curve was chosen. This shear rate
is in the range that occur in the mouth when eating viscous or semi-solid
foods [Daget, et al., "Creamy Perception I. In Model Dessert Creams", J.
Texture Studies, 18, 367-388 (1987)].
The viscosities at 50 s.sup.-1 are plotted vs. concentration in FIG. 27 and
compared with similar results for a xanthan/protein complex dispersion.
The viscosity of both the xanthan/protein and carboxymethyl
cellulose/protein complex dispersions appear to have exponential
dependences on concentration.
The pH dependence of the viscosity was measured at both 5 and 13 weight
percent total solids content. A plot of viscosity vs. pH in FIG. 28 shows
that viscosity of the 13 weight percent dispersion is very dependent on pH
with a minimum located between pH 3.5 and 4.0. The viscosity rises sharply
at higher pH, changing over a factor of 1000 from pH 3.66 to 5.51. The
viscosity vs. pH curve of a 5 weight percent dispersion of the
carboxymethyl cellulose/protein complex shows smaller but similar trends.
The viscosity at 50 s.sup.-1 is plotted as a function of NaCl concentration
and compared with similar results for a xanthan/egg white+whey protein
complex microfragment dispersion in FIG. 29. Addition of salt to a
dispersion of the microfragmented carboxymethyl cellulose/protein complex
decreases the viscosity up to a salt concentration of 0.72%, but above
that level the viscosity begins to increase with increasing concentration.
In contrast, the viscosity of a xanthan/protein complex dispersion
continues to decrease and level off at about 2 weight percent salt
concentration. Food products such as salad dressings, table spreads and
sauces may contain 2 percent or more by weight salt.
The electrophoretic mobility of 0.5 mg/ml colloidal carboxymethyl
cellulose/protein complex and xanthan/protein complex dispersions were
measured on a PenKem System 3000 electrokinetic analyzer at various pH's
and 25.degree. C. The isoelectric point is the pH where the
electrophoretic mobility is zero. The mobility unit is 10E-08
meter/sec/volt/meter. The electrophoretic mobility of the carboxymethyl
cellulose/protein complex and the components are shown as a function of pH
in FIG. 21, while the electrophoretic mobility of a microfragmented
carboxymethyl cellulose/egg white+whey protein complex is shown in
comparison to that of a microfragmented xanthan/egg white+whey protein
complex in FIG. 23.
The following table shows that the carboxymethyl cellulose/protein complex
has a higher protein/gum ratio for the egg white and whey protein employed
than the xanthan/protein complex.
______________________________________
Microfragmented Polysaccharide/
Egg White/Whey Protein Complexes
Protein/Gum
Particle Size
Polysaccharide Ratio (microns)
______________________________________
Xanthan 3.5/1 7.12
CMC 8/1 6.68
(Carboxymethyl
cellulose)
______________________________________
EXAMPLE 19 - Chitosan
A microfragmented, cationic polysaccharide/protein aqueous dispersion was
prepared using chitosan as the cationic polysaccharide. Five grams of WPC
(Kraft Whey Protein Concentrate containing 35% protein) was suspended in
560 ml of distilled water in an Osterizer blender at 22.degree. C., and 5
grams of KDEW (Kraft Blue Label Dried Egg White) were added into the WPC
suspension with stirring to from a protein solution. To the protein
solution was added 1.25 gram of chitosan (100 mesh, Broshell Inc.) and the
gum/protein mixture was stirred for 3 minutes (at 22.degree. C.). The pH
of the chitosan/WPC/KDEW mixture was adjusted to 7.1 (the pH before
acidification), 6.3, 6.0, 5.5, 4.5, 4.0 and 3.5. Chitosan/WPC/KDEW
mixtures at different pH's were centrifuged at 1000.times.g. at 22.degree.
C. for 10 minutes. The supernatant liquids were decanted and used for
turbidity and protein quantification by using a Lowry method. The
chitosan/protein complex appeared to precipitate most readily between pH
6.3 and pH 5.5, at which (pH's) the complex is sufficiently stable that
boiling is not necessary to stabilize the complex for many uses.
The turbidity of the supernatant solutions as a function of pH was
determined, as shown by FIG. 30, indicating the maximal precipitation
(minimum solubility) of the chitosan/egg albumen/whey protein complex was
between pH 6.3 and pH 5.5, while based on the protein determination of the
supernatant solutions, the maximal precipitation (or minimal solubility)
was determined (FIG. 31) to be about pH 5.5. The electrophoretic mobility
of the chitosan/protein complex was determined as a function of pH, as
previously described, together with respective mobilities of the various
components, as shown in FIG. 32. The precipitated chitosan/protein complex
was stabilized by boiling in water for 5 minutes, and subjected to
microfragmentation as described in Example 17 to provide a 5 weight
percent aqueous dispersion. The dispersion was concentrated by
centrifugation to provide a concentrated dispersion.
A photomicrograph of the microfragmented chitosan complex dispersion
particles is shown in FIG. 33.
EXAMPLE 20
Carrageenan Complex
A carrageenan--egg white--whey protein complex was prepared in a manner
substantially similar to that of Example 17, except that kappa carrageenan
was used instead of carboxymethyl cellulose. The complex was boiled for 5
minutes, cooled, washed and fluidized by using a CD150 cell disruptor.
This fluidized carrageenan--egg white--whey protein complex was adjusted
to pH 4.0 and then centrifuged at 10,000.times.g. and at 10.degree. C. for
20 minutes. The fluidized carrageenan-protein complex (after
centrifugation) was white, smooth, creamy and had fat-like
characteristics. A photomicrograph of the kappa carrageenan/protein
complex dispersion particles is shown in FIG. 35. A graphical
representation of the relationship of electrophoretic mobility of a
carrageenan/egg white/whey protein complex as a function of pH, together
with the respective mobilities of the individual components is shown in
FIG. 36.
EXAMPLE 21--Gellan
A gellan--egg white--whey protein complex was prepared in a manner
substantially similar to that of Example 17, except that gellan was used
instead of carboxymethyl cellulose. The complex was boiled for 5 minutes,
cooled, washed and fluidized by using a CD150 cell disruptor. This
fluidized gellan--egg white--whey protein complex was adjusted to pH 4.0
and then centrifuged at 10,000.times.g. and at 10.degree. C. for 20
minutes. The fluidized gellan-protein complex (after centrifugation) was
white, smooth, creamy and has fat-like characteristics. A photomicrograph
of the gellan/protein complex is shown in FIG. 37. The graphical
representation of the relationship of electrophoretic mobility of a
gellan/egg white/whey protein complex as a function of pH, together with
the respective mobilities of the individual components is shown in FIG.
38.
EXAMPLE 21A
The microfragmented ionic polysaccharide/protein dispersions prepared in
Examples 17-21 were subjected to analysis of protein/polysaccharide ratio,
maximum particle size and shape, and protein denaturation as follows:
(Dntd OVa and Dntd BLG are abbreviations for denatured and cross-linked
ovalbumin and beta-lactoglobulin, respectively.)
______________________________________
Protein:Gum Protein Particle Maximum
Ratio Denaturation Dimension
______________________________________
Carboxymethyl Cellulose/Protein Complex
8:1 (7.9:1) Dntd OVA 54% 0.5- 3.0 .mu.m by SEM
Dntd BLG 18% 1 .times. 2 .mu.m common
Kappa Carrageenan/Protein Complex
8:1 (8.3:1) Dntd OVA 69% 0.2 .times. 1.0 .mu.m by SEM
Dntd BLG 43% 0.4 .mu.m common
Gellan/Protein Complex
5:1 (4.6:1) Dntd OVA 81% 0.1 .times. 1.0 .mu.m by SEM
Chitosan/Protein
n.d. Dntd OVA 90% 0.1- 0.2 .mu.m by SEM
______________________________________
EXAMPLE 21B
Mayonnaise-like salad dressings and frozen desserts were prepared using
each of the concentrated, 5 microfragmented aqueous dispersions of
Examples 18-21, by substitutinq the concentrated microfragmented
dispersion for the major portion of the fat components. The preparation of
the model mayonnaise emulsion of Example 18A has been described herein
above. The respective, microfragmented dispersions of Examples 19, 20 and
21 Were each formulated in model mayonnaise emulsion in the same manner as
described in Example 18A, with substitution of the respective concentrated
dispersion of each Example for the CMC/protein dispersion. The mayonnaise
products had the following viscosity.
______________________________________
Mayonnaise Emulsion
Droplet Size Viscosity
Polysaccharide (Microns) (Haake Units)
______________________________________
Xanthan gum/protein
4.48 1860
control
CMC/protein Example 18
3.89 780
Carrageenan/protein
6.32 500
Example 20
Gellan/protein 10.9 380
Example 21
Chitosan/protein
8.03 320
Example 19
______________________________________
EXAMPLE 22
In order to prepare a polysaccharide/protein complex by emulsification in a
hydrophobic working liquid, a water-in-oil emulsion was prepared from the
following components:
______________________________________
Soybean Oil 1382 g.
Emulsifier component
118 g.
Aqueous Phase component
1140 g.
0.1 M HCl 360 g.
3000 g.
______________________________________
Emulsifier Aqueous Phase (complex
Component Forming) Component
______________________________________
Soy Lecithin
6 g. Xanthan Gum 6.25 g.
Myverol 1892
12 g. Kraft dried egg white
25 g.
Soybean Oil
100 g. WPC 25 g.
118 g. Water 2150 g.
2206.25 g.
______________________________________
The emulsifier component was prepared by heating and stirring the
emulsifiers with the soybean oil. The aqueous phase complex forming
component was prepared by mixing water in Hobart Mixer (med, 55 on
Variac), adding first WPC, then dried egg white and finally xanthan gum
followed by thorough mixing. The emulsifier component was added to the
major portion of soybean oil while stirring at 200 rpm using 2-blade (A310
& R500) agitator with a Lightnin mixer. The speed was increased to 600 rpm
before addition of the aqueous phase was begun, and this speed was further
increased to 900 rpm to produce emulsification. The resulting water-in-oil
emulsion was stirred for about 10 minutes. The 0.1M HCl was added to the
emulsion to acidify the aqueous phase and stirring continued at 900 rpm (5
min). Stirring was reduced to 600 rpm, then increased to I200 rpm before
stopping.
The amount of hydrochloric acid was chosen to exceed the optimum amount by
a factor of 2 (based on the aqueous phase) to ensure that a pH level of
3-4 is achieved in substantially all aqueous phase drops. There will
actually be a distribution of pH at any finite time after addition of HCl
and it is desired to lower the pH adequately in all droplets.
Diluted hydrochloric acid was used to increase the volume of the
acid-containing phase added, so as to ensure a more even distribution.
Lecithin was used as an emulsification agent to lower interfacial tension,
and Myverol 1892 was used to stabilize the emulsion.
Fibers were observed to form rapidly upon addition of acid. The emulsion
began to separate slowly after agitation was stopped. This instability
after complex precipitation is an advantage in product separation.
About 1100 g. of the mix was centrifuged at 10,000 rpm for 30 min at
10.degree. C. Oil, water and pellets are obtained. Oil and water are
poured off and the solid fibers isolated. The fibers were very creamy and
without grittiness. The remainder of the mix was observed to separate over
time to a water layer and a layer of oil plus fibers. Instead of
hydrochloric acid, gluconodelta lactone may also be used as a slow
acidulant. Similarly, an oil soluble edible acid, such as malic or acetic
acid, or mixtures thereof may be used in the organic phase.
The size of the fibers is constrained by the size of the emulsion droplets
in the method described in this Example. By controlling the size of the
emulsion droplets, the size of the fiber particles may be readily
controlled. The energy requirement for forming an emulsion is much lower
than for microfragmentation of preformed fibers, and accordingly, less
work is necessary to produce particles of a preselected volume through
emulsification of the aqueous fiber forming solution utilized in high
shear microfragmentation of the preformed fibers.
EXAMPLE 23
A xanthan gum/protein complex was prepared by emmulsification in oil using
monoglyerides and solid lecithin as the emulsifer component, to provide a
small droplet size in the emulsion. To reduce off-flavors associated with
commercial grade lecithin, a purified solid lecithin (Centrolex F) was
used with monoglyceride in the production of the emulsion. The resulting
product had lower astringency, lower acid/sour flavor, and lower mouth
drying than a control sample.
To prepare the complex, subcomponents A and B were utilized in the
preparation procedure as follows:
Sub A - To 103g of soybean oil in a beaker were added 12g Myverol 1892
monoglyceride and 3g of solid lecithin (Centrolex F), which were heated
gently to dissolve the components.
Sub B - To 2150 g of water in a blender container were added 20 g of
diafiltered whey protein, 50 g Kraft dried egg white and 13 g xanthan gum
while blending briefly after the addition of each component. The mixture
was blended well after all the components were added.
In a three-neck flask were combined 1382 g soybean oil with 118 g of the
emulsifier mix (Sub A). The mixture was stirred using a Tekmar
homogenizer. The protein-gum mix (Sub B) was slowly added while continuing
to homogenize the sample. The homogenizer was able to break the
protein-gum mix into small droplets. When the emulsion looked quite milky,
the acid component (Sub C) was added. As fibers were formed heating the
sample with a heat mantle was begun. Heat to about 98.degree. C. to
denature the fibers. Stop heating and remove the mentle and immerse the
flask in a bucket of ice to cool to room temperature. The xanthan
gum/protein complex can be obtained by centrifugation to separate the oil
and concentrate the solids as in the previous example.
The sample was analyzed as follows:
______________________________________
Sample pH 3.21
Protein/Gum Ratio 3.14
% Solids 22.84
Dry Basis Comp. (%)
Fat 56.70
Protein 34.75
Gum 10.84
Total Basis Comp. (%)
Fat 12.95
Ash 0.00
Moisture 77.16
Nitrogen 1.27
Carbohydrate 3.30
Protein Comp. (%)
cross-linked beta-lactoglobulin
10
(% of total beta-lactoglobulin)
crosslined ovalbumin (% of total
50
ovalbumin)
Ovalbumin 53
beta-lactoglobulin 16
alpha-lactalbumin 8
ovalbumin/beta-lactoglobulin ratio
3.61
______________________________________
Analysis of this sample showed a moderate concentration of retained soybean
oil in the product, which may be reduced by improving the efficiency of
the centrifugation process.
The generation of complex fibers in this manner in situ in an oil phase may
be used in the preparation of oil based products such as margarines and
analog cheeses in which the complex-containing emulsion is used in product
preparation to provide a product with reduced calorie content.
EXAMPLE 24
Xanthan gum/protein fibers were made from several proteins lacking
sulfhydryl groups to provide low astringency fibrous complexes. The
proteins used to prepare the complexes were lysozyme, polylysine and
gelatin.
As indicated, lysozyme (a protein containing no sulfhydryl groups, but 4
disulfide bonds was used to prepare xanthan protein complexes as follows:
Formula
450 ml distilled water
1.0 g xanthan gum
5.0 g lysozyme (from chicken egg white)
The xanthan gum was dissolved in the water in a blender. Fibers formed in
the blender upon the addition of lysozyme (added slowly with blending)
because of the high isoelectric point of lysozyme. The mixture was then
placed in a beaker (the fibers floated to the top), and 5.5 ml of 1N HCl
was added without stirring. The mixture was then stirred and poured onto
cheesecloth in a collander. The fibers were collected and boiled 15
minutes in 150 ml distilled water. The fibers were placed on cheesecloth
and rinsed extensively with distilled water. Excess water was squeezed out
by hand.
The sample was tasted by an informal panel of persons having varying
degrees of sensitivity to astringency. The panel detected very little
astringency.
A second complex was prepared using polylysine (a protein containing only
lysine residues and accordingly no sulfhydryl groups or disulfide bonds),
according to the following procedure:
Formula
90 ml. distilled water
0.2 g xanthan gum
1.0 g poly-DL-lysine hydrobromide
The xanthan gum was dissolved in the water using a small blender. The
polylysine was blended in for 4 minutes. Fibers formed without adding acid
to lower the pH because of the high isoelectric point of the polylysine.
The mixture was poured onto cheesecloth and the fibers were collected and
boiled in 30 ml distilled water for 5 minutes. The fibers were placed on
cheesecloth and rinsed extensively with distilled water. Excess water was
squeezed out by hand. Informal taste panel testing detected little or no
astringency.
A third complex was prepared using gelatin (a protein containing
substantially no sulfhydryl groups or disulfide bonds) according to the
following procedure:
Formula
2800 ml. distilled water
6.25 g xanthan gum
31.9 g gelatin (Type B, 225 bloom)
The xanthan gum was dissolved in the water in a large blender. The gelatin
was added and blended for 5 minutes. The mixture was poured into a beaker
and 100 ml of 1N HCl was added. The mixture was stirred and allowed to sit
one hour. Fibers were not boiled and were placed in the cold overnight,
resulting in gelling. The gel-like material was washed on cheesecloth with
deionized water, resulting in dissolution of most of the gelatinous
material, and leaving material having more of a fibrous nature (but not as
fibrous as xanthan/protein complexes as described herein). Excess water
was squeezed out by hand. The sample was tasted by an informal taste
panel. Most of the panel detected little or no astringency in the sample.
EXAMPLE 25
Proteolysis may also be utilized to provide polysaccharide/protein
complexes possessing reduced astringency. In this regard, treatment of an
egg-white/whey protein concentrate protein blend with the proteolytic
enzyme Pronase brought about changes in the material which allowed fibers
to be made with xanthan gum which had reduced astringency, in accordance
with the following procedure:
Proteolysis Formula
2000 ml tap water, 35.degree. C.
50 g dried egg white (Kraft)
50 g whey protein concentrate
0.2 g Type XXV Pronase E (Streptomyces Griseus proteolytic enzyme from
Sigma Chemical Company.)
The dried egg white, whey protein concentrate and Pronase proteolytic
enzyme were dissolved in the water and incubated at 35.degree. C. for 5
hours to provide a proteolyzed egg white/whey protein solution. The
proteolyzed protein solution was used to prepare fibers with xanthan gum,
in accordance with the following formula and procedure:
Fiber Formula
1800 ml distilled water
6.25 g xanthan gum
1000 ml of the proteolyzed egg white-whey protein concentrate solution
Two batches of xanthan/protein fibers were made from each proteolysis batch
according to the following procedure. Xanthan gum was dissolved in the
water in a blender and 1000 ml of the proteolyzed solution was added and
mixed for 5 minutes. The mixture was placed in a beaker and 35 ml of 1N
HCl was added and the mixture stirred gently while fibers were forming.
After several minutes, the fibers were drained on cheesecloth, then boiled
in distilled water. The fibers were placed on cheesecloth and rinsed with
distilled water, squeezing out the excess water by hand.
Two batches of fibers were pooled and homogenized with a Tekmar homogenizer
for 45 minutes, then microfluidized in the M110 microfragmentation
homogenizer at high pressure, generally as described in Example 1 for 70
minutes. The pH of the microfluidized material was adjusted to 3.5 with 1N
HCl before centrifuging and collectinq the pelleted material.
Both the fibers and the microfluidized fibers (the latter evaluated at 10%
solids) were evaluated to be considerably less astringent than control
xanthan/protein complex products prepared without proteolysis treatment.
EXAMPLE 26
Three batches of coated xanthan/protein microfragmented emulsion coated
fibers were prepared in accordance with a method similar to that
illustrated in FIG. 1, but including various coating components. The
respective batches had soybean oil (5 weight percent dry basis), sodium
stearoyl lactylate (SSL, 5 weight percent dry basis), and soybean oil (2.5
weight percent dry basis) in combination with SSL (2.5 weight percent dry
basis) added in the last chamber of the (Pentax) mixer prior to
microfragmentation with a high shear homogenizer (CD 150 cell disruptor).
A substantial improvement in drying in the mouth was found for the SSL
coated sample. Acid/sour flavor and acid aftertaste was most improved in
the combination coating.
Model emulsions of viscous products were prepared and tasted informally.
Some tasters thought that astringency was reduced in the coated materials
while others noted no improvement.
Other food grade surfactants may be utilized to provide a surface coating,
such as monoglycerides, ethoxylated monoglycerides and polyglycerol
esters. Higher melting and oxidatively stable fats.
EXAMPLE 27
Xanthan/protein fibers prepared generally in accordance with the method of
FIG. 1 were boiled for 5 minutes in sodium phosphate buffer (50 mM, pH
8.0) or in buffer containing 100 micro moles L-cystine per gram of fibers
(dry basis), approximately a five-fold excess over the theoretical level
of sulfhydryl groups in the protein. After cooling, the fibers were
reacidified to about pH 3, washed and subjected to partial homogenization
but not full microfluidization. Only 5% of the sulfhydryl groups remained
in the cystine treated samples whereas 35% remained when boiled alone. An
informal taste panel scored the cystine treated samples as less astringent
than boiled without cystine. Boiling alone caused a slight reduction in
astringency.
EXAMPLE 28
A microfluidized aqueous dispersion of xanthan/whey protein+egg white
complex as prepared in accordance with Example 1 (without thin film
concentration) having a total solids content of about 5 weight percent was
well mixed with a 2 weight percent sodium alginate solution in a 2:1
weight:weight ratio of the complex dispersion to the alginate solution, to
provide 15 kg of blended mixture. A 20 weight percent calcium acetate
solution (250 grams) was added slowly to the 15 kg of the blended mixture.
The mixture formed a gel, which was reduced to small particle size by a
Tekmar high speed rotary homogenizer. The broken gel was passed twice
through a CD 30 Cell Disruptor at about 12,000 PSI to yield a calcium
alginate coated, microfragmented xanthan/protein complex dispersion.
The coated dispersion was treated with a protease (P-7026 protease from
Aspergillus Sojoe, purchased from Sigma) to determine the accessibility of
the protein component of the coated microfragments of the dispersion. The
water soluble peptides and amino acids released by protease hydrolysis
were determined by absorption measurement at 280 nanometers wavelength. An
untreated control sample of the xanthan/whey protein+egg white protein
complex was also treated with the protease and subjected to absorption
measurement at 280 nanometers to measure peptide and amino acid
concentration in solutions following proteolysis.
The calcium alginate coated microfragments produced significantly less
peptides and amino acids than the control. The absorption at 280
nanometers with the control sample was more than 10 times greater than the
absorption of the calcium alginate coated sample at 280 nanometers.
Calcium pectinate-coated dispersions may similarly be prepared, using
pectin, instead of alginate.
It is noted that mild proteolytic treatment of both the coated and the
uncoated microfragmented aqueous dispersions may produce microfragments
having fragment surfaces which have a reduced concentration of protein
sulfhydryl groups at the surface of the fragments. Direct proteolytic
treatment of aqueous dispersions of ionic polysaccharide/protein complexes
containing a nonionic polysaccharide component such as cornstarch, which
is not affected by the enzyme, may particularly benefit from such
treatment.
EXAMPLE 29
A reduced calorie, substantially fat-free frozen dessert product was
prepared utilizing a microfragmented xanthan/protein complex prepared in a
manner similar to that of Example 3, except that the complex is prepared
from xanthan gum, egg white and skim milk. Xanthan gum, skim milk or
ultrafiltered skim milk and dried egg white or frozen egg whites are
suspended in water at a temperature in the range of 70.degree.-80.degree.
F. to provide a solution solids content of 2.7 percent in the fiber
forming solution. The formulation of the starting material is calculated
to obtain a xanthan to egg protein to milk protein ratio of 1:1.55:2.3 or
1:1.5:3.0. Two typical formulations follows: (a) xanthan gum, 1.35 lbs;
frozen egg whites, 19 lbs; skim milk, 78 lbs; and water, 237 lbs or (b)
xanthan gum 1.35 lbs, dried egg whites, 2.69 lbs, ultrafiltered skim milk
26 lbs, and water 289 lbs.
Processing
The processing procedures for preparing such bland dispersions are
substantially the same as Example 3 with the following exceptions: The pH
of fiber formation is targeted at pH 3.7; and the total solids in the
starting mix is about 2.7 percent. The concentration of solids after
stabilization and draining is typically between 7.5 percent and 11.5
percent. The fibers are microfragmented at this concentration using a
Gaulin cell disruptor at high pressure. The resulting material is either
used at the above solids content or is concentrated by centrifugation.
The complex has a protein to gum ratio of 2.5 to 3.5. The proteins as
determined from gel electrophoresis include caseins (@67 percent), whey
proteins (@10 percent) and ovalbumin (@7 percent). The crosslinked
ovalbumin was greater than 80 percent. The aqueous microfragmented
dispersion is quite bland. The frozen dessert product had the following
composition:
______________________________________
Ingredients Wt. %
______________________________________
Water 65.3
Milk Solids not Fat 12.5
Sucrose Solids 12.0
Corn Syrup Solids 8.1
Microfragmented xanthan/
2.0
protein complex
Butter Flavor 0.1
100.0
______________________________________
In preparing the frozen dessert mix, the water, milk solids not fat (in the
form of condensed skim milk having 35% by weight total solids), sucrose,
corn syrup and flavorings were blended in a Lanco high shear mixer. After
mixing, the blended ingredients were preheated to 150.degree. F. and
homogenized by passing the mixture under pressure through a two-stage
homogenizer at a pressure drop of 2000 psi in the first stage and 500 psi
in the second stage of the homogenizer. The homogenized mix was then
pasteurized at 185.degree. F. for 30 seconds in a high temperature short
time (HTST) processing unit of Crepaco, Cedar Rapids, Iowa. The
homogenized, pasteurized mix was next cooled to 40.degree. F. and
discharged into a storage container. The mix was aged for four hours at
40.degree. F. before freezing.
The unflavored white mix was frozen in an Emery Thompson (Bronx, N.Y.)
batch freezer. The unflavored frozen mix (100% overrun - 50% air) was
discharged into packaging containers at 19.degree.-23.degree. F. and
hardened at -20.degree. F. It had desirable, creamy characteristics
provided by the xanthan/protein microfragmented complex dispersion
component.
EXAMPLE 30
A reduced fat buttermilk-type dressing was prepared using a microfragmented
xanthan/egg white-skim milk complex dispersion like that used in Example
29. The buttermilk dressing was made using the following ingredients:
______________________________________
Ingredients Wt. %
______________________________________
Water 44.863
Sugar 2.000
Fluid Buttermilk 20.000
25 DE Corn Syrup 15.000
Salt 1.800
Gums 0.900
Sorbic Acid 0.200
Lactic Acid/Vinegar 3.250
Food Grade Coloring Agent
0.200
Flavorings 4.700
Xanthan/egg white-skim
4.000
milk complex
EDTA 0.007
Spices 0.080
Hydrogenated Soybean Oil
3.000
______________________________________
The dressing was prepared by first dry blending the gums, coloring agent
and sugar. The dry blended gum/coloring agent/sugar mixture was then
slowly added to the xanthan/skim milk protein complex dispersion in a
Hobart mixer. The buttermilk, flavorings, salt, EDTA, sorbic acid, water
and corn syrup were then added to the xanthan/protein complex blend,
followed by mixing for two minutes. The lactic acid and vinegar were next
added to the blend, followed by mixing for one minute. The hydrogenated
soybean oil was added, followed by homogenization or mixing using a high
shear mixing device. The spices were blended in after emulsification to
produce a buttermilk-type dressing product having only about 3 weight
percent fat, but having the rich, fat-like mouthfeel and texture of a
product substantially higher in fat content.
EXAMPLE 31
A reduced calorie, substantially fat-free French dressing was prepared
using a microfragmented xanthan/egg white-skim milk complex dispersion
like that used in Example 29. The French dressing was made using the
following ingredients:
______________________________________
Ingredients Wt. %
______________________________________
Water 53.689
Sugar 10.500
25 DE Corn Syrup 20.000
Salt 1.850
Tomato Paste 1.500
Garlic Juice 1.000
Gums 0.550
Sorbic Acid 0.200
Vinegar 6.000
Food Grade Coloring Agent
0.020
Spices/Flavorings 0.685
Xanthan/egg white-skim
4.000
milk complex
EDTA 0.006
______________________________________
The reduced calorie French dressing was prepared by dry blending the gums,
coloring agent and sugar. The dry blended mixture was slowly added to the
aqueous xanthan/egg white-skim milk microfragmented dispersion in a Hobart
mixer. The spices/flavorings, salt, EDTA, sorbic acid, water and corn
syrup were then added to the resulting blend, followed by mixing for two
minutes. The tomato paste, garlic juice and vinegar were then added to the
blend and mixed for one minute. The finished blend was homogenized or
mixed using a high shear mixing device, to provide a reduced calorie
fat-free French dressing having a rich texture and mouthfeel similar to
that conventionally provided by a substantial vegetable oil component.
EXAMPLE 32
A number of Complexes of xanthan with egg white and whey protein were
prepared with equal proportions of xanthan gum, dried egg whites (KDEW,
Blue Label), and whey protein concentrate (containing 35% by weight
protein). To prepare the complexes, 18.75 grams of whey protein
concentrate were dispersed in 2,800 ml of deionized water in a Waring
blender (while blending at 1200 rpm and 22.degree. C.), followed by adding
18.75 g dried egg white in the whey protein concentrate dispersion while
blending in the Waring blender under the same conditions. Subsequently,
18.75 g xanthan gum was added to the mixture while blending, followed by
blending the gum/protein mixture for 5 minutes. Thirty-five milliliters of
1 molar hydrochloric acid was added to the mixture while blending under
the same conditions to obtain gel-like complex. The xanthan/protein
complex to was allowed to synerese. The gel-like complex was separated
from the supernatant and boiled for 5 minutes. The gel-like
xanthan/protein complex was smooth, creamy, had a fat-like mouthfeel and
was less astringent than the xanthan/protein complex of the type generally
described in Example 3. This boiled and drained gel-like xanthan/protein
complex was centrifuged at 10,000.times.g and 5.degree. C. for 20 minutes.
This centrifuged pellet of the complex was even creamier than the
microfragmented complex and had little astringency.
The microfluidized xanthan/egg white gel was found to be blander than the
microfluidized xanthan/egg white/whey protein concentrate gel. Both
microfluidized gel-like complexes were smoother and blander than a product
like that of Example 3. The electrophoretic mobility of the xanthan/egg
white gel as a function of pH is shown in FIG. 16, as compared to a
product like that of Example 3.
Both gel-like xanthan/dried egg white-whey protein concentrate and
xanthan/KDEW/WPC complexes were microfluidized using a microfluidizer
Model 110Y of Biotechnology Development Corporation, at an input pressure
of about 15-18,000 psi as described in Example 3. The microfragments of
these two complexes were micro rod-like, and very negatively charged
(i.e., pI<2.0). They dispersed readily in water. The high negativity of
these microfragments may account for their high dispersability and
smoothness.
EXAMPLE 33
A xanthan/egg white-caseinate gel complex is made in the same manner as
described in Example 32 from xanthan gum, egg white and skim milk at a
1:1:1 weight ratio of xanthan gum, egg white and skim milk protein. The
undenatured microfragmented xanthan/egg white-skim milk gel was formed
into a model mayonnaise emulsion like that of Example 18 at a 50 weight
percent oil replacement level, and compared to a control model mayonnaise
emulsion using a heat stabilized microfragmented xanthan/egg white-whey
protein concentrate (1:4:4) like that of Example 3.
Photomicrographs of the heat stabilized fibrous xanthan/protein complex
control (FIG. 40) with the non-heat stabilized xanthan/egg white-whey
protein concentrate (1:1:1) microfragmented gel (FIG. 41) show the gel
product has a smooth, relatively uniform dispesion of the xanthan/protein
complex between the oil droplets of the mayonnaise emulsion.
EXAMPLE 34
A low fat comminuted meat hot dog product was prepared utilizing a
microfragmented xanthan/egg white-whey protein complex dispersion like
that of Example 3, from the following ingredients:
______________________________________
Ingredient Grams
______________________________________
Pork 57.0
Beef chuck 106.0
Pork fat 17.0
Salt 9.0
White pepper .4
Ginger .3
Onion powder .2
Nonfat dairy milk solids
8.0
Dry mustard .5
Ground coriander seed
.6
Nitrite .7
Hickory smoke 2.0
Xanthan gum 3.0
xanthan/egg white-whey
30.0
protein complex
Ice 20.0
______________________________________
The hot dogs were prepared by blending the pork, beef and fat in a food
processor about 40 seconds (until it formed a cohesive mass) followed by
the ice and blending for another 30 seconds. The xanthan/protein complex
microfragment dispersion was then blended in for another 30 seconds,
followed by the spices, nonfat dairy milk solids and gum with blending
about 30 seconds. The nitrite was then blended well for 20 seconds. The
meat emulsion was then put in a pastry bag and squeezed into hog casing in
the form of hot dogs, removing all air bubbles. The resulting hot dogs
were then boiled 10 minutes in 190.degree. F. water.
______________________________________
Analytical Information
Low Fat Hot Dogs Control Hot Dogs
______________________________________
69.20% Moisture 55.50% Moisture
2.53% Nitrogen 1.94% Nitrogen
11.00% Fat 28.00% Fat
15.80% Protein 12.00% Protein
______________________________________
EXAMPLE 35
A reduced fat peanut butter having a triglyceride content of only 35 weight
percent was prepared using a microfragmented xanthan/egg white-whey
protein complex dispersions like that of Example 3. The ingredients used
were as follows:
______________________________________
80.0 g Peanut Flour #174 (Seabrooks)
100.0 g Peanut Flour #160 (Seabrooks)
12.0 g Peanut Flour #251 (Seabrooks)
140.0 g Water
______________________________________
These components were blended in a food processor and let standing 10
minutes to soften the flour. The following ingredients were then blended
in the food processor with the flour/water mixture until smooth
(approximately 45 seconds).
______________________________________
89.5 g Xanthan/egg white-whey protein
concentrate (15% solids)
60.0 g Glucose (bakery)
12.0 g Sucrose (white sugar)
6.5 g salt
3.8 g baking soda
2.5 g peanut butter flavor
100.0 g unstabilized peanut butter
______________________________________
An 80% fat reduced peanut butter was similarly maade from the following
ingredients:
______________________________________
80.0 g Peanut Flour #174 (Seabrooks)
112.0 g Peanut Flour #160 (Seabrooks)
144.5 g Water
89.5 g xanthan/egg white-whey protein
concentrate (21% solids)
37.0 g Dextrose
15.0 g White granulated sugar
7.5 g Salt
3.8 g Baking soda
2.5 g Peanut butter flavor
______________________________________
In preparing the 80% fat reduced peanut butter, the peanut butter flour is
blended with water in a food processor and permitted to stand for 10
minutes to soften the flour. The microfragmented xanthan/protein complex
and flavorings are then well blended into the mixture, to provide a blend
having the following composition:
20.0% Protein
13.3% Fat
22.4% Carbohydrate
44.3% Water
778 calories/490.8 g
EXAMPLE 36
A cream of mushroom soup was prepared using a microfragmented xanthan/egg
white-whey protein complex dispersion like that of Example 3, from the
following ingredients:
______________________________________
2.00 g Olive Oil (6% Fat)
60.00 g Onion
30.00 g Celery
4.00 g Minced garlic
200.00 g Sliced mushrooms
3.00 g Dried Porcini mushrooms
30.00 g White Wine
.15 g Black pepper
3.00 g Salt
4.00 g Sugar
.40 g Thyme
450.00 g Chicken stock
46.30 g Xanthan/egg white-whey protein
complex (16.6% solids)
245.00 g Skim milk
18.00 g All purpose flour
1.20 g Butter buds
6.00 g Nonfat dairy milk solids (low heat)
1.50 g Chopped Parsley
______________________________________
The onion, garlic and celery are sauteed in oil over medium heat for 3
minutes The mushrooms and Porcini are added and are sauteed 5 minutes or
until mushrooms release all moisture and begin to brown, and the mixture
is deglazed with white wine. The pepper, salt, sugar, thyme and stock are
added and simmered for 15 minutes Separately, milk and the xanthan complex
are mixed in a blender until smooth, and the nonfat milk solids, flour and
butter buds are combined with mixing in the xanthan complex mixture. The
sauteed components and the xanthan complex blend are combined and boiled
for 3 minutes. Parsley is added.
EXAMPLE 37
Less leavened baked goods such as baked brownies having reduced fat may be
made using microfragmented ionic polysaccharide/protein complexes as
described herein. In this regard, brownies having 0.4 weight percent fat
were prepared from microfragmented xanthan/egg white-egg protein
concentrates of the type described in Example 3, using the following
ingredients:
______________________________________
Amount Ingredient
______________________________________
70.0 g Condensed skim milk
1.0 g GP 911 FMC gum
26.0 g Cocoa powder (Gerkins 10-12%)
187.0 g Glucose
20.0 g Granulated sugar (sucrose)
2.7 g Water
55.3 g Xanthan/protein complex
dispersion (20% solids)
3.7 g Vanilla
10.0 g Creme de cocoa
1.0 g Carmi chocolate flavor
40.0 g Granulated sugar
36.0 g Egg white
40.0 g Cake flour
11.0 g All purpose flour
25.0 g Chopped walnuts
20.0 g Granulated sugar
______________________________________
To prepare the brownies, the gum was thoroughly dissolved in the milk, and
the cocoa powder, glucose and 20 g sugar were added, followed by water and
the xanthan/protein complex. The ingredients were whisked thoroughly. The
vanilla, creme de cocoa and chocolate flavor were then added. Egg whites
were beaten 20 seconds, and 40 g sugar were added until soft peaks formed.
Flour was sifted into the chocolate mix, and folded in until not
completely incorporated. Egg whites were folded in until still slightly
ribbony. The mix was baked at 350.degree. F. in an oven for 24 minutes.
EXAMPLE 38
A reduced fat chocolate cake (1.0% fat) was similarly prepared using a
microfragmented xanthan/egg white-whey protein complex like that of
Example 3, using the following ingredients:
______________________________________
Amount Ingredient
______________________________________
28.0 g Gerkins cocoa
65.0 g Concentrated skim milk
75.0 g Sucrose
50.0 g Glucose syrup
40.0 g Dextrose (Staley 300)
58.0 g Xanthan/egg white-whey protein
concentrate complex (15% Solids)
62.0 g Cake flour
2.0 g Instant starch
4.0 g Vanilla
10.0 g Creme de cocoa
5.5 g Baking powder
48.0 g Egg whites
40.0 g Sugar
______________________________________
To prepare the leavened cake, the xanthan/protein complex was blended with
the milk, in which was also blended the cocoa, sugars, glucose syrup,
vanilla and creme de cocoa. The dry ingredients (baking powder, starch,
flour) were sifted into the cocoa mixture and very gently stirred into the
bowl. The egg whites were then folded in with care not to overwhip. The
mix was placed in 9" round cake pan sprayed with a pan release agent baked
and at 360.degree. F. for 23 minutes.
EXAMPLE 39
Sweet Douqh Product
A sweet dough product was prepared utilizing a microfragmented anisotropic
xanthan/protein complex dispersion containing hydrated xanthan/whey
protein concentrate-egg protein complex microfragments of the type
described in Example 1 in aqueous dispersion and having a solids content
of 20.0 weight percent, based on the total weight of the dispersion. In
preparing the sweet dough product, the following ingredients were
utilized:
______________________________________
Ingredients Weight %
______________________________________
Sponge
Flour, bread 30.00
Yeast, compressed
2.00
Yeast food 0.25
Water (75.degree. F.)
16.00
Dough
Flour, bread 17.00
Water (45.degree. F.)
10.00
Yeast, compressed
1.00
Salt 1.00
Sugar 7.00
Dextrose 3.00
Nonfat dry milk 2.00
Xanthan/protein 7.00
Dispersion
Emulsifier (Mono-
.25
Diglycerides)
Egg Yolk Solids 3.25
Flavor .25
Total 100.00
______________________________________
To produce the sweet dough product, the sponge ingredients were mixed
together for 3 minutes on low speed in a N-50 Hobart mixer using a dough
hook. The sponge (78.degree. F.) was set for one hour. To mix the dough,
an A-200 Hobart mixer was used with a 12 quart bowl and dough hook. The
dough flour, water, yeast, sugar, dextrose, milk, emulsifier, egg yolk
solids and flavor and sponge were placed in the bowl and mixed for 30
seconds on low, then 7 minutes on 2nd speed. The salt and microfragmented
anisotropic xanthan/protein dispersion was then added to the bowl, and
mixed for 30 seconds on low, then 2 minutes on 2nd speed to full
development. Dough temperature--80.degree. F.
The dough was divided into 284 gram pieces which were given a 10 minute
rest period after rounding. The dough pieces were then made up into
typical bread-type loaves and placed in a lightly greased loaf pan of
appropriate size. The molded dough pieces were then placed in a proof box
at 95.degree. F. temperature and 80% relative humidity for 60 minutes till
top of dough was 3/4" above pan. The proofed dough pieces were then baked
in a reel oven at 400.degree. F. for 21 minutes. The loaves were depanned
immediately and cooled for 1 hour.
The sweet dough product was analyzed to have the following composition:
______________________________________
Moisture 39.35%
Fat 4.62
Aw (water activity)
.94
pH 5.54
______________________________________
The sweet dough product had a finer grain, darker crust color, increased
volume and somewhat softer texture than a typical control product
utilizing shortening (fat) in place of the microfragmented anisotropic
xanthan/protein dispersion. The sweet dough product also has a reduction
in calories and fat content compared to the typical control product.
EXAMPLE 40
Improved Sweet Douqh Product
An improved sweet dough product was prepared utilizing a microfragmented
anisotropic xanthan/protein complex dispersion containing hydrated
xanthan/whey protein-egg white protein complex microfragments in aqueous
dispersion and having a solids content of 20.0 weight percent, based on
the total weight of the dispersion. This dispersion is added to a typical,
fat containing control formulation as a dough product improver, which
includes, but not limited to, the attributes of dough strengthening,
volume enhancing, crumb softening, moisture retention and shelf life
extending. In preparing the new improved sweet dough product, the
following ingredients were utilized:
______________________________________
Ingredients Weight %
______________________________________
Sponge
Flour, bread 30.00
Yeast, compressed 2.00
Yeast food 0.25
Water (75.degree. F.)
16.00
Dough
Flour, bread 17.00
Water (45.degree. F.)
10.00
Yeast, compressed 1.00
Salt 1.00
Sugar 7.00
Dextrose 3.00
Nonfat dry milk 2.00
Shortening 7.00
Emulsifier (Mono- .25
Diglycerides)
Egg Yolk Solids 3.25
Flavor .25
100.00
Microfragmented 3.00
Anisotropic Xanthan/
Protein Dispersion
Total 103.00
______________________________________
To produce the improved sweet dough product, the sponge ingredients were
mixed together for 3 minutes on low speed in a N-50 Hobart mixer using a
dough hook. The sponge (78.degree. F.) was set for one hour. To mix the
dough, an A-200 Hobart mixer was used with a 12 quart bowl and dough hook.
The dough flour, water, yeast, sugar, dextrose, milk, emulsifier, egg yolk
solids, flavor and sponge were placed in the bowl and mixed for 30 seconds
on low, then 7 minutes on 2nd speed. The salt and shortening and
microfragmented anisotropic xanthan/protein dispersion were then added to
the bowl, and mixed for 30 seconds on low, then 2 minutes on 2nd speed to
full development. Dough temperature--80.degree. F.
The dough was divided into 284 gram pieces which were given a 10 minute
rest period after rounding. The dough pieces were then made up into
typical bread-type loaves and placed in a lightly greased loaf pan of
appropriate size. The molded dough pieces were then placed in a proof box
at 95.degree. F. and 80% relative humidity for 70 minutes until the top of
dough was 3/4" above the pan. The proofed dough pieces were then baked in
a reel oven at 400.degree. F. for 21 minutes. The loaves were depanned
immediately and cooled for one hour.
The improved sweet dough product was analyzed to have the following
composition:
______________________________________
Moisture 35.06%
Fat 10.79%
Aw (water activity)
.93
pH 5.56
______________________________________
The improved sweet dough product had a somewhat finer grain, darker crust
color, increased volume and softer texture than a typical control product
not utilizing the beneficial attributes of the microfragmented anisotropic
xanthan/protein dispersion added as a dough/product improver.
An improved baked goods product was prepared utilizing a microfragmented
anisotropic xanthan/protein complex dispersion of the type described in
Example 1 containing the hydrated xanthan/whey protein-egg white protein
complex microfragments in aqueous dispersion and having a solids content
of 20.0 weight percent, based on the total weight of the dispersion. This
dispersion is added to a typical, fat containing control formulation as a
dough product improver, which includes, but not limited to, the attributes
of dough strengthening, volume enhancing, crumb softening, moisture
retention and shelf life extending. In preparing the new improved sweet
dough product, the following ingredients were utilized:
______________________________________
Ingredients Weight %
______________________________________
Sponge
Flour, bread 30.00
Yeast, compressed 2.00
Yeast food 0.25
Water (75.degree. F.)
16.00
Dough
Flour, bread 17.00
Water (45.degree. F.)
10.00
Yeast, compressed 1.00
Salt 1.00
Sugar 7.00
Dextrose 3.00
Nonfat dry milk 2.00
Shortening 7.00
Emulsifier (Mono- .25
Diglycerides)
Egg Yolk Solids 3.25
Flavor .25
100.00
Microfragmented 3.00
Anisotropic Xanthan/
Protein Dispersion
Total 103.00
______________________________________
To produce the improved baked goods product, the sponge ingredients were
mixed together for 3 minutes on low speed in a N-50 Hobart mixer using a
dough hook. The sponge (78.degree. F.) was set for one hour. To mix the
dough, an A-200 Hobart mixer was used with a 12 quart bowl and dough hook.
The dough flour, water, yeast, sugar, dextrose, milk, emulsifier, egg yolk
solids, flavor and sponge were placed in the bowl and mixed for 30 seconds
on low, then 7 minutes on 2nd speed. The salt and shortening and
microfragmented anisotropic xanthan/protein dispersion were then added to
the bowl, and mixed for 30 seconds on low, then 2 minutes on 2nd speed to
full development. Dough temperature--80.degree. F.
The dough was divided into 284 gram pieces which were given a 10 minute
rest period after rounding. The dough pieces were then made up into
typical bread-type loaves and placed in a lightly greased loaf pan of
appropriate size. The molded dough pieces were then placed in a proof box
at 95.degree. F. and 80% relative humidity for 70 minutes until the top of
dough was 3/4" above the pan. The proofed dough pieces were then baked in
a reel oven at 400.degree. F. for 21 minutes. The loaves were depanned
immediately and cooled for one hour.
The improved baked goods product was analyzed to have the following
composition:
______________________________________
Moisture 35.06%
Fat 10.79%
Aw (water activity)
.93
pH 5.56
______________________________________
The improved baked goods product had a somewhat finer grain, darker crust
color, increased volume and softer texture than a typical control product
not utilizing the beneficial attributes of the microfragmented anisotropic
xanthan/protein dispersion added as a dough/product improver.
EXAMPLE 41
Danish Product/Danish Roll-In Product
Danish products are sweet dough products, but with a portion of their fat
content rolled-in as layers (roll-in) between dough. This has a layering,
leavening effect which produces a flaky product. The cell structure is
oval and horizontal, as opposed to round as in the sweet dough product.
A danish roll-in product for danish product was prepared utilizing a
microfragmented anisotropic xanthan/whey protein-egg protein complex
dispersion of the type described in Example 1 containing the hydrated
xanthan/protein complex microfragments in aqueous dispersion and having a
solids content of 20.0 weight percent, based on the total weight of the
dispersion. In preparing the new danish product/danish roll-in product,
the following ingredients were utilized:
______________________________________
Weight %
______________________________________
Danish Product
Dough 85.00 - 75.00
Roll-In 15.00 - 25.00
100.00 - 100.00
Dough
Flour, Patent 47.00
Sugar 8.00
Shortening, all purpose
8.00
Egg yolk solids 3.00
Yeast, compressed 3.00
Nonfat dry milk 2.00
Flavor .50
Water (45.degree. F.)
26.75
Mono & Diglycerides
1.00
100.00
Roll-In
Shortening, all purpose
46.00
Microfragmented anisotropic
50.00
xanthan/protein dispersion
Polysaccharides 4.00
100.00
______________________________________
To produce the danish roll-in product, the polysaccharides were mixed into
the shortening on a Hobart N-50 mixer with paddle. The microfragmented
anisotropic xanthan/protein dispersion was then added and thoroughly
blended in. This mixture will now be referred to as the "roll-in". It was
then set aside to attain a temperature of 65.degree. F. The dough
ingredients were all added to a 12 quart bowl and mixed on low speed for 6
minutes on an A-200 Hobart mixer with dough hook. Dough temperature was
about 65.degree. F. The dough pieces was dropped out on a floured bench
top and formed to a rectangular shape. The dough was rolled out by hand
using a wooden rolling pin to a size of approximately 15" by 30". The
"roll-in" was applied to the right 2/3's of the dough in an even manner to
form a continuous sheet of "roll-in". The left 1/3 of the plain dough was
then folded over the center 1/3. The right 1/3 (with roll-in) was then
folded over and on top of the already folded 1st and 2nd thirds. This
3-fold process was repeated 3 more times with a 20 minute rest period in a
38.degree. F. retarded after the last 3 folds. This is a typical procedure
for production of dough pieces for danish baked goods. The dough piece was
then sheeted (rolled) out to approximately 1/8" thick and cut into
3".times.8" test strips and placed on sheet pans. The danish product was
allowed to rise in a proof box at 95.degree. F. temperature and 80%
relative humidity for 60 minutes. They were then baked at 380.degree. F.
for 12 minutes and cooled.
The danish product (roll-in) was analyzed to have the following
composition:
______________________________________
Moisture 26.15%
Fat 20.65%
Aw (water activity)
.94
pH 5.28
______________________________________
The danish product/danish roll-in product exhibited a somewhat oval grain
structure and layering effect similar to that of a typical danish control
product using a full fat roll-in. The danish product/danish roll-in
product, however, has a reduction in calories and fat content compared to
the typical control product.
EXAMPLE 42
Bread-Type Product
Bread-type products are yeast and chemically leavened baked goods
including, but not limited to, white bread, hearth breads, variety breads,
ethnic breads, buns, rolls, english muffins, bagels and pizza-type
products.
A bread-type product was prepared utilizing a microfragmented anisotropic
xanthan/whey protein-egg white protein complex dispersion of the type
described in Example 1 containing the hydrated xanthan/protein complex
microfragments in aqueous dispersion and having a solids content of 20.0
weight percent, based on the total weight of the dispersion. In preparing
the new bread-type product, the following ingredients were utilized:
______________________________________
Ingredients Weight %
______________________________________
Flour, patent 54.57
Water (65.degree. F.)
35.47
Yeast, compressed 1.64
Yeast food .13
Salt 1.09
Sugar, granulated 3.82
milk, non-fat, dry 1.64
microfragmented anisotropic
1.64
xanthan/protein dispersion
100.00
______________________________________
To produce the bread type product, the straight dough method was used
wherein all the ingredients were mixed together at one time using a 12
quart bowl with dough hook on an A-200 Hobart mixer. Mix times were: low
for 1 minutes, then 2nd speed for 8 minutes to development. Dough
temperature--81.degree. F. The dough was allowed to ferment in a
90.degree. F. fermentation box for 90 minutes. The dough was punched down
and divided into 454 gram dough pieces and rounded. Following a 10 minute
rest period, the dough pieces were made up into typical bread-type loaves
and placed in a lightly greased loaf pan of appropriate size. The molded
dough pieces were then placed in a proof box at 95.degree. F. temperature
and 80% relative humidity for 60 minutes until the top of the dough was 1"
above pan. The proof dough pieces were then baked in a reel oven at
430.degree. F. for 22 minutes. The loaves were depanned immediately and
cooled for 1 hour.
The bread type product was analyzed to have the following composition:
______________________________________
Moisture
43.75%
Fat 6.84%
Aw .95
pH 5.32
______________________________________
The bread-type product had a coarser grain and reduced volume in comparison
to a typical control product utilizing shortening (fat) in place of the
microfragmented anisotropic xanthan/protein dispersion. The bread-type
product would have a reduction in calories and fat content compared to the
typical control product.
EXAMPLE 43--Cake Product
Cake products are chemically and mechanically leavened baked goods
including, but not limited to sheet cakes, loaf cakes, pound cakes, sponge
cakes, angel food cakes, muffins, snack cakes, doughnuts and eclairs.
A cake product was prepared utilizing a microfragmented anisotropic
xanthan/whey protein-egg white protein complex dispersion containing the
hydrated xanthan/protein complex microfragments in aqueous dispersion and
having a solids content of 20.0 weight percent, based on the total weight
of the dispersion. In preparing the new cake product, the following
ingredients were utilized:
______________________________________
Ingredients Weight %
______________________________________
Sugar 28.0
Flour, cake 24.0
Microfragmented anisotropic
11.0
xanthan/protein dispersion
emulsifier (mono & 1.0
diglycerides)
Eggs, whole 12.50
Nonfat, dry milk 2.00
Water 19.25
Baking powder 1.00
Salt .75
Flavor, vanilla .50
100.00
______________________________________
To produce the cake product, a 12 quart bowl with paddle was used on a
Hobart A-200 mixer. The flour, sugar, milk, baking powder and salt were
placed in a bowl and dry blended. The microfragmented anisotropic
xanthan/whey protein-egg white protein dispersion, emulsifier, flavors and
1/3rd of the water were added and the components were mixed to a paste in
low. The eggs and remaining water were gradually mixed in at law and
second blending speed, and batter was blended smooth. Deposit 454 grams of
batter in lightly greased 8" cake pan, baked in reel oven at 350.degree.
F. for 35 minutes. Cool cake product in the pan for 1 hour.
The cake product was analyzed to have the following composition:
______________________________________
Moisture 36.12%
Fat 4.29%
Aw (water activity)
.90
pH 6.83
______________________________________
The cake product had a finer, dense grain, lighter crust color, decreased
volume and a very firm texture in comparison to a typical control product
utilizing shortening (fat) in place of the microfragmented anisotropic
xanthan/protein dispersion. The cake product would also have a reduction
in calories and fat content compared to a typical control product.
EXAMPLE 44
Pie shell products are baked goods for, but not limited to, fruit pies,
filled pies, tarts, pie shells, fried pies and meat pies.
A pie shell product was prepared utilizing a microfragmented anisotropic
xanthan/protein complex dispersion containing the hydrated xanthan/protein
complex microfragments in aqueous dispersion and having a solids content
of 20.0 weight percent, based on the total weight of the dispersion. In
preparing the new pie shell product, the following ingredients were
utilized.
______________________________________
Ingredients Weight %
______________________________________
Flour, pastry 54.00
Salt .50
Dextrose 1.50
Microfragmented anisotropic
14.00
xanthan/protein dispersion
Water (40.degree. F.)
16.00
Shortening, all purpose
14.00
100.00
______________________________________
To produce the pie shell product, a N-50 Hobart mixer was used with a
cutter paddle. The flour, dextrose, salt and microfragmented anisotropic
xanthan/protein dispersion and shortening were placed in a bowl and dry
blended. Mix with cutter blade in low was carried out until shortening is
in very fine lumps. All water was incorporated and mixed to form an even
mass which was then divided into 4 pieces. Each piece was rolled out to
approximately 1/8" thick and laid over a 9" pie pan. Another pie pan was
placed on top. Excess dough was cut off. Shells were baked in a reel oven
at 400.degree. F. for 10 minutes. Shells then turned upside down, bottom
pan removed and baked another 10
The pie shell product was analyzed to have the following composition:
______________________________________
Moisture 13.64%
Fat 20.41%
Aw (water activity)
.86
pH 5.43
______________________________________
The pie shell product had a dense, tough texture in comparison to a typical
full fat pie shell. The pie shell product would have a reduction in
calories and fat content compared to a typical control product.
EXAMPLE 45
Cookie Product
Cookie products include, but are not limited to drop cookies, wire-cut
cookies, cutting machine cookies, rotary molded cookies and filled
cookies.
A cookie product was prepared utilizing a microfragmented anisotropic
xanthan/whey protein-egg white protein complex dispersion of the type
described in Example containing the hydrated xanthan/protein complex
microfragments in aqueous dispersion and having a solids content of 20.0
weight percent, based on the total weight of the dispersion. In preparing
the new cookie product, the following ingredients were utilized:
______________________________________
Ingredients Weight %
______________________________________
Sugar 29.00
Salt .50
Baking Soda .25
Flavor .25
Shortening, all purpose
15.00
Microfragmented anisotropic
5.00
xanthan/protein dispersion
Eggs 10.00
Flour, pastry 40.00
100.00
______________________________________
To produce the cookie product, the sugar, salt, baking soda, flavor,
shortening and microfragmented anisotropic xanthan/protein dispersion were
placed in a 5 quart bowl and mixed with a paddle on a N-50 Hobart mixer
for 2 minutes on low. The eggs were added and mixed for 1 minute on low.
The flour was added and mixed for 2 minutes on low.
The dough was rolled into tube-like dough pieces about 1" in diameter, ten
gram pieces were cut off and placed on baking paper on a cookie baking
pan. Cookies were baked at 420 F. for 8 minutes and then cooled.
The cookie product was analyzed to have the following composition:
______________________________________
Moisture 8.33%
Fat 19.64%
Aw (water activity)
.52
pH 8.39
______________________________________
The cookie product had approximately the same spread diameter, a slightly
darker bottom color and a more spongy, open grain texture than a typical
full fat control product. The cookie products also had a reduction in
calories and fat content compared to the typical control product.
EXAMPLE 46
Icing Product
Icing products include, but are not limited to, icings for baked products,
"buttercream" icings, flat icings or any other glazings, frostings.
An icing product was prepared utilizing a microfragmented anisotropic
xanthan/whey protein-egg white protein complex dispersion containing the
hydrated xanthan/protein complex microfragments in aqueous dispersion and
having a solids content of 20.0 weight percent, based on the total weight
of the dispersion. In preparing the new icing product, the following
ingredients were utilized:
______________________________________
Ingredients Weight %
______________________________________
Powdered sugar 55.60
Nonfat dry milk 4.00
Salt .20
Flavor .20
Microfragmented anisotropic
22.50
xanthan/protein dispersion
Shortening, all purpose
17.50
100.00
______________________________________
To produce the icing product, the powdered sugar, dry milk and salt were
dry blended in a 5 quart bowl on a N-50 Hobart mixer with paddle for 10
seconds on low. The flavor, shortening and microfragmented anisotropic
xanthan/protein dispersion were added and mixed 1 minute on low, then 1
minute on 2nd speed to smooth the icing.
The icing product was analyzed to have the following composition:
______________________________________
Moisture 15.08%
Fat 17.10%
Aw (water activity)
.7
pH 5.37
______________________________________
The icing product was similar, but softer in texture than a typical full
fat icing. The icing product had a reduction in calories and fat content
compared to the typical control
EXAMPLE 47
Filling-Topping Product
Filling-topping products for baked goods include, but are not limited to,
crumb fillings, sugar/flour/fat fillings, creme or cream fillings, cheese
fillings, fruit fillings, crumb toppings, sugar/fat/flour toppings, creme
or cream toppings, cheese toppings and fruit toppings.
A filling-topping product was prepared utilizing a microfragmented
anisotropic xanthan/whey protein-egg white protein complex dispersion
containing the hydrated xanthan/protein complex microfragments in aqueous
dispersion and having a solids content of 20.0 weight percent, based on
the total weight of the dispersion. In preparing the filling-topping
product, the following ingredients were utilized:
______________________________________
Ingredients Weight %
______________________________________
Sugar 25.00
Molasses 4.00
Salt .50
Shortening, all purpose
12.50
Microfragmented anisotropic
12.50
xanthan/protein dispersion
Flavor/spice .50
Flour pastry 44.00
Water 1.00
100.00
______________________________________
To produce the filling-topping product, the sugar, molasses, salt,
shortening, flavor/spice and microfragmented anisotropic xanthan/protein
dispersion were added to a 5 quart bowl and mixed for 2 minutes on low on
a N-50 Hobart mixer with paddle. The flour and water were then added and
mixed in for 30 seconds until a general incorporation had taken place
suitable for a topping. Continued mixing and increased water content would
result in a less viscous, smooth material suitable as a filling.
The filling-topping product was analyzed to have the following composition:
______________________________________
Moisture 15.78%
Fat 11.33%
Aw (water activity)
.77
pH 5.28
______________________________________
The filling-topping product was drier and more dense than a typical
filling-topping control product. The filling-topping product tended to
spread and liquify more and seemed tougher than a control product when
baked. The filling-topping product would also have a reduction in calories
and fat content compared to the typical control product.
EXAMPLE 48
In order to determine the effects of coating of ionic
polysaccharide/protein complexes with polysaccharides and lipids, an
aqueous microfragmented dispersion of xanthan/egg white-whey protein
concentrate complex of the type described in Example 3 was coated with a
variety of gums and lipid components in a number of separate runs. In each
run, the microfragmented xanthan/protein complex having a solids content
of 8.48% weight percent was combined with water and the indicated gums,
lipid or combination of gum and lipid to give a final concentration of
8.00% weight percent total solids in the aqueous dispersion:
Run 1) microfragmented xanthan/protein complex+iota carrageenan (10:1
weight ratio)
Run 2) microfragmented xanthan/protein complex+locust bean gum (10:1 weight
ratio)
Run 3) microfragmented xanthan/protein complex+lecithin (5:1 weight ratio)
Run 4) microfragmented xanthan/protein complex+locust bean gum (10:0.67
weight ratio)+xanthan (10:0.33 Weight ratio)
Run 5) microfragmented xanthan/protein complex+xanthan (10:0.67 weight
ratio)+iota carrageenan (10:0.33 weight ratio)
Run 6) microfragmented xanthan/protein complex+lecithin (25:1.4 weight
ratio)+xanthan (25:1.1 weight ratio)
The weight ratio of microfragmented xanthan/protein complex solids to the
respective gum and/or lipid coating agent for each of the above runs is
given in parenthesis. To prepare the coated samples of each run, the gums
were mixed with the microfragmented xanthan/protein complex by placing the
microfragmented xanthan/protein complex in a blender and mixing while
slowly adding the dry gum. Mixing was continued for 15 minutes to allow
sufficient time for hydration of the gum. When lecithin was added, the
mixing was done with a Tekmar homogenizer at approximatgely 100.degree. F.
The lecithin was added slowly to prevent clumping. The pH of all samples
was adjusted to 4.0.
The mixture of the microfragmented xanthan/protein complex with the
indicated gums and/or lecithin were evaluated by a panel trained in
quantitative descriptive analysis. A control sample of the microfragmented
xanthan/protein complex without coating agent(s), but diluted with water
from 8.48 to 8 percent total solids content was also evaluated for
comparison purposes. The point scale used was continuous and was scored
using a full-scale value of 60 points. Differences in mean scores were
evaluated by ANOVA followed by the Bonferroni test for multiple
comparisons. A wide variety of attributes were evaluated by the panel, the
following is a selection which illustrates some of the improvements made
by coating the microfragmented xanthan/protein complex with gums and/or
lecithin:
__________________________________________________________________________
Wet Paper Odor
Acid/Sour Flavor
Chalky Flavor
Astringent
weak.fwdarw.strong
weak.fwdarw.strong
weak.fwdarw.strong
slightly.fwdarw.extrem
ely
__________________________________________________________________________
Control 6.6 -- 16.2 -- 9.3 -- 6.7 a
Run 1 with Iota carrageenan
2.8 b 6.5 b 1.4 a 2.2 b
Run 2 with Locust bean gum
7.1 16.3 8.8 5.0
Run 3 with Lecithin 4.9 21.7 2.3 a 7.3
Run 4 with Iota Carrageenan + Xanthan
6.1 11.7 3.8 b 2.8 c
Run 5 with Locust Bean Gum + Xanthan
3.3 c 10.4 5.3 4.3
Run 6 with Lecithin + Xanthan
4.2 11.3 3.0 b 4.9
__________________________________________________________________________
Initial Response Response after 3 Minutes
Chalky Mouthfeel
Drying in the Mouth
Astringent
Drying in the Mouth
slightly.fwdarw.extremely
slightly.fwdarw.extremely
slightly.fwdarw.extremely
slightly.fwdarw.extrem
ely
__________________________________________________________________________
Control 12.0 -- 27.8 -- 3.2 -- 9.8 a
Iota Carrageenan 1.6 a 14.3 a 1.8 b 3.5 a
Locust Bean Gum 1.8 a 19.3 b 1.4 a 4.9 b
Lecithin 3.8 a 18.4 a 1.8 b 6.5
I-Carrageenan + Xanthan
2.1 a 17.1 a 1.4 a 5.8 c
Locust Bean Gum + Xanthan
3.1 a 12.0 a 1.6 a 5.1 b
Lecithin + Xanthan 3.3 a 18.8 b 2.3 c 4.9
__________________________________________________________________________
b
The letters following the mean values for the various coated
microfragmented xanthan/protein complexes indicate they are significantly
different from the value for the microfragmented xanthan/protein complex
control by the following level of significance: a (p<0.01), b (p<0.05), c
(p<0.10). No letter indicates that there was no significant difference
from the control.
It is noted that all of the coatings significantly reduced chalky
mouthfeel, drying in the mouth and astringent aftertaste (3 minutes).
In order to provide data to determine whether coating the microfragmented
xanthan/protein complex with a polysaccharide reduces drying mouthfeel at
neutral pH as well as at acidic pH, the microfragmented xanthan/protein
complex was adjusted to pH 6.5 with dilute sodium hydroxide and a portion
was then coated with xanthan gum. In addition, another portion of the
microfragmented xanthan/protein complex was coated with xanthan gum and
part of this mixture was adjusted to pH 6.5 with dilute sodium hydroxide.
The adjustment of pH was done by slow addition of 0.1M NaOH while mixing
the microfragmented xanthan/protein complex rapidly. Xanthan was added
slowly as a dry powder while mixing, and mixing was continued for 15
minutes to allow for hydration of the xanthan. The solids of all the
mixtures was adjusted to about 4.5%, and the untreated microfragmented
xanthan/protein complex was adjusted to pH 4.0 and 4.5% solids.
A research laboratory panel tasted the mixtures (including the untreated
control) blind, in random order, and rated them on the characteristics of
drying in the mouth, astringency and off-flavors on a scale from 0 to 7
(indicating none to severe). The mean scores for drying in the mouth were
as follows:
______________________________________
Mean Score
Significant Level of Difference
Drying in from uncoated
from uncoated
the Mouth xanthan/protein
xanthan/protein
none >extreme
at pH 4 at pH 6.5
______________________________________
Uncoated,
5.5 -- 0.10
pH 4.0
Uncoated,
2.8 0.10 --
pH 6.5
+xanthan,
2.2 0.05 none
pH 4.0
+xanthan 1.7 0.01 none
.fwdarw. pH 6.5
.fwdarw. pH 6.5 +
1.2 0.01 0.05
xanthan
______________________________________
While the present invention has been particularly described with respect to
various embodiments, it will be appreciated that various modifications and
adaptations may be made based on the present disclosure, which are
regarded to be within the spirit and scope of the present invention.
Various of the features of the invention are set forth in the following
claims.
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